WO2022211008A1 - Metal paste for joining, and method for manufacturing joined body - Google Patents
Metal paste for joining, and method for manufacturing joined body Download PDFInfo
- Publication number
- WO2022211008A1 WO2022211008A1 PCT/JP2022/016454 JP2022016454W WO2022211008A1 WO 2022211008 A1 WO2022211008 A1 WO 2022211008A1 JP 2022016454 W JP2022016454 W JP 2022016454W WO 2022211008 A1 WO2022211008 A1 WO 2022211008A1
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- temperature
- liquid phase
- bonding
- metal
- metal paste
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- 239000002184 metal Substances 0.000 title claims abstract description 130
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 130
- 238000005304 joining Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 110
- 150000001879 copper Chemical class 0.000 claims abstract description 53
- 150000001412 amines Chemical class 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 230000008034 disappearance Effects 0.000 claims description 20
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- -1 carboxylic acid copper salt Chemical class 0.000 claims description 7
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 235000011837 pasties Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 12
- 230000000630 rising effect Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 3
- 229940071536 silver acetate Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- RXWOHFUULDINMC-UHFFFAOYSA-N 2-(3-nitrothiophen-2-yl)acetic acid Chemical compound OC(=O)CC=1SC=CC=1[N+]([O-])=O RXWOHFUULDINMC-UHFFFAOYSA-N 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- SEKCXMNFUDONGJ-UHFFFAOYSA-L copper;2-ethylhexanoate Chemical compound [Cu+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SEKCXMNFUDONGJ-UHFFFAOYSA-L 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
- B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3618—Carboxylic acids or salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
Definitions
- the present invention relates to a bonding metal paste used for bonding members together, and a method for manufacturing a bonded body using this bonding metal paste.
- semiconductor devices such as LEDs and power modules have a structure in which a semiconductor element is bonded onto a circuit layer made of a metal member.
- a method using a solder material is widely used as disclosed in Patent Document 1, for example.
- Patent Document 2 proposes a technique of forming a plating film and a Sn-based solder layer, alloying them by heat treatment to form an alloy layer, and mounting an electronic component on a substrate.
- Patent Document 3 proposes a technique for bonding electronic components such as semiconductor elements onto a circuit using a metal paste containing metal powder.
- a bonding layer made of a conductive sintered body is formed, and an electronic component such as a semiconductor element is bonded to a circuit via this bonding layer.
- the bonding layer is composed of a metal sintered body, it has excellent thermal conductivity and excellent bonding reliability.
- the bonding layer when the bonding layer is formed of a sintered metal, the bonding layer can be formed under relatively low temperature conditions and the melting point of the bonding layer itself is high, so that the bonding strength does not significantly decrease even in a high temperature environment.
- a liquid phase does not occur in the temperature rising process during joining. Therefore, self-alignment of the relative positions of the members could not be achieved.
- the present invention has been made in view of the above-mentioned circumstances, and is capable of generating a liquid phase in the temperature rising process during bonding, adjusting the relative positions of members by self-alignment, and providing a heat-resistant member. It is an object of the present invention to provide a bonding metal paste capable of forming a bonding layer composed of a metal sintered body with excellent bonding strength and bonding strength, and a method for manufacturing a bonded body using this bonding metal paste.
- the metal paste for bonding of the present invention contains a metal powder, a copper salt, an amine, and an alcohol, and the ratio of the weight A of Cu in the copper salt to the weight B of the metal powder is A/ B is in the range of 0.02 or more and 0.25 or less, it is pasty within the temperature range of 15 ° C. or more and 35 ° C. or less, and a liquid phase is generated in the process of raising the temperature from 35 ° C., and the liquid phase It is characterized in that the liquid phase disappears in the process of increasing the temperature above the production temperature, and a metal sintered body is formed above the liquid phase disappearance temperature.
- the metal powder, the copper salt, the amine, and the alcohol are included, the paste is in the form of a paste within the temperature range of 15° C. or higher and 35° C. or lower, and the liquid phase is formed in the process of increasing the temperature from 35° C. can be printed or dispensed or pin-transferred in a working environment at room temperature.
- a liquid phase is generated in the temperature rising process during bonding, and the relative positions of the bonding members can be self-aligned.
- the metal powder since the metal powder is contained, even if a liquid phase occurs, a distance can be secured between the members, and a sufficient bonding layer can be formed.
- the liquid phase disappears at the liquid phase generation temperature or higher, and the metal sintered body is formed at the liquid phase disappearance temperature or higher, so the bonding strength does not decrease even in a high temperature environment. It is possible to form a bonding layer excellent in Further, since the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less, the liquid phase is sufficiently In addition, the density of the metal sintered body after sintering becomes sufficiently high, and strong bonding strength can be realized.
- the metal powder is preferably one or two of silver and copper.
- the metal powder is one or two of silver and copper, it is possible to form a bonding layer that is particularly excellent in heat conduction.
- the copper salt preferably contains an organic carboxylic acid copper salt.
- the metal complex can be reliably formed by adding it together with the amine, and the liquid phase can be reliably formed during the temperature rising process during bonding. can appear.
- the metal paste for bonding of the present invention may contain two or more of the copper salts.
- a single copper salt does not form a paste at a temperature range of 15°C or higher and 35°C or lower
- a combination of two or more kinds of the copper salt can form a paste at a temperature range of 15°C or higher and 35°C or lower. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
- the said amine contains a linear alkylamine.
- the amine is supposed to contain a straight-chain alkylamine, it is possible to reliably form a metal complex by adding it together with a copper salt, and a liquid phase reliably appears during the heating process during bonding. can be made
- the amine may be composed of two or more kinds of amines.
- a mixture of two or more amines can be combined to form a paste in a temperature range of 15°C to 35°C. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
- the alcohol may consist of two or more alcohols.
- the paste viscosity is not optimal for a single alcohol depending on the method of use, it is possible to adjust the paste viscosity to a suitable value by combining two or more alcohols.
- the metal paste for bonding of the present invention preferably contains a silver salt in addition to the metal powder, copper salt, amine and alcohol.
- the silver salt reacts with the amine to form a silver complex, and the silver complex is reduced by alcohol to generate nano-sized silver particles, making it possible to further improve the bonding strength.
- a method for manufacturing a bonded body of the present invention is a method for manufacturing a bonded body in which a first member and a second member are bonded, wherein the first member and the second member are The above-described bonding metal paste is disposed between the first member and the second member, and the temperature is raised in a state where the bonding metal paste is disposed between the first member and the second member. and the second member, the temperature is raised to the liquid phase generation temperature or higher to disappear the liquid phase, and the temperature is further raised to the liquid phase disappearance temperature or higher to form a metal sintered body. and joining the first member and the second member.
- the metal paste for bonding is disposed between the first member and the second member in a temperature range of 15° C. or higher and 35° C. or lower, and then the temperature is raised. Since the surface tension of the liquid phase causes self-alignment of the relative positions of the first member and the second member. In addition, since the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body, a bonding layer made of the metal sintered body is formed. It is possible to manufacture a bonded body excellent in heat resistance and bonding strength.
- a metal sintered body that generates a liquid phase in the temperature rising process during bonding can adjust the relative position of members by self-alignment, and has excellent heat resistance and bonding strength. It is possible to provide a bonding metal paste capable of forming a bonding layer composed of the above metal bonding paste, and a method for manufacturing a bonded body using this bonding metal paste.
- FIG. 2 is a flowchart showing a method for joining joined bodies using a joining metal paste according to an embodiment of the present invention.
- FIG. 2 is an explanatory diagram of a method of joining a joined body using a joining metal paste according to an embodiment of the present invention
- FIG. 4 is an explanatory diagram of a mounting position of a Si chip and a confirmation method of self-alignment in an example
- FIG. 4 is an explanatory diagram of a method for evaluating the liquid phase formation temperature in Examples.
- the metal paste for bonding of the present embodiment is used when manufacturing a bonded body by bonding the first member and the second member. For example, it is used when bonding a semiconductor element (second member) as an electronic component to a circuit layer (first member) of an insulated circuit board.
- the bonding metal paste of the present embodiment contains metal powder, copper salt, amine, and alcohol. Furthermore, the metal paste for joining of this embodiment may contain a silver salt. In addition, in the metal paste for bonding of the present embodiment, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less.
- the metal paste for bonding according to the present embodiment is paste-like within a temperature range of 15° C. or higher and 35° C. or lower.
- the liquid phase disappears and the metal sintered body is formed at a temperature equal to or higher than the liquid phase disappearance temperature.
- the metal paste for bonding contains a copper salt and an amine, so that a metal complex (copper complex) is formed by mixing these.
- This metal complex becomes a paste within a temperature range of 15° C. or higher and 35° C. or lower, and a liquid phase is generated by further heating.
- the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is less than 0.02, the content of the copper salt becomes insufficient and the liquid is There is a risk that the phase will not be sufficiently formed and the self-alignment property will be impaired.
- the weight ratio A/B exceeds 0.25, the liquid phase is excessively generated, the amount of volatilized organic matter increases, the density of the metal sintered body after firing decreases, and the bonding strength may decrease.
- the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is set within the range of 0.02 or more and 0.25 or less.
- the above weight ratio A/B is preferably 0.04 or more, more preferably 0.06 or more.
- the above weight ratio A/B is preferably 0.20 or less, more preferably 0.15 or less.
- the metal powder is preferably one or two of silver and copper. Moreover, it is preferable that the metal powder has an average particle size within the range of 100 nm or more and 3 ⁇ m or less.
- a copper salt may be added together with an amine to form a copper complex.
- an organic carboxylic acid copper salt as the copper salt.
- copper (II) acetate monohydrate, copper citrate 2.5 hydrate, copper 2-ethylhexanoate, etc. can be used, and as the copper salt, copper (II) acetate It is preferred to use the monohydrate.
- the amine should just form a copper complex by being added with a copper salt.
- the amine preferably contains a linear alkylamine. Specifically, dodecylamine, tetradecylamine, stearinamine, aminodecane, etc. can be used, and dodecylamine is preferably used as the amine. In addition, in this embodiment, two or more types of amines may be contained as amines.
- Glycerin, ⁇ -terpineol, diethylene glycol (DEG) 2-ethyl 1,3-hexanediol (EHD) and the like can be used as alcohols.
- DEG diethylene glycol
- EHD 2-ethyl 1,3-hexanediol
- you may contain two or more types of alcohol as alcohol.
- silver salts include silver acetate, silver oxalate, silver propionate, silver myristate, silver butyrate, and the like. In particular, it is preferable to use silver acetate.
- the content of the metal powder is preferably in the range of 25 mass% or more and 75 mass% or less.
- the content of the copper salt is within the range of 4 mass % or more and 16 mass % or less.
- the content of amine is preferably in the range of 16 mass% or more and 54 mass% or less.
- the alcohol content is preferably in the range of 1 mass % or more and 10 mass % or less.
- the content of the silver salt is preferably in the range of 0.1 mass % or more and 12 mass % or less.
- each content is when the metal paste for joining is 100 mass%.
- the metal paste for bonding of the present embodiment can be produced by weighing the above-mentioned metal powder, copper salt, amine, alcohol, and optionally silver salt so as to obtain a predetermined composition and mixing them. can.
- FIG. 1 a bonded body 10 (semiconductor device) in which a first member 11 (circuit layer of an insulated circuit board) and a second member 12 (semiconductor element) are bonded via a bonding layer 15 is manufactured. .
- the bonding metal paste 20 of the present embodiment is arranged between the first member 11 and the second member 12 .
- the bonding metal paste 20 is printed on the bonding surface of the first member 11 by screen printing.
- the coating thickness is preferably in the range of 20 ⁇ m or more and 500 ⁇ m or less.
- the first member 11 and the second member 12 are laminated via the bonding metal paste 20 and heated to the liquid phase generation temperature or higher.
- the copper complex formed by the copper salt and amine contained in the bonding metal paste 20 is liquefied, and a liquid phase is formed between the first member 11 and the second member 12 . 21 is generated.
- the surface tension of the liquid phase 21 causes the relative positions of the first member 11 and the second member 12 to be self-aligned.
- the temperature at which the liquid phase 21 is generated is preferably in the range of over 35° C. and 100° C. or less.
- the formation temperature of the liquid phase 21 is more preferably less than 100°C.
- the bonding metal paste 20 contains a silver salt, a silver complex is formed by the silver salt and the amine.
- the holding temperature should be in the range of 100° C. or more and 200° C. or less, and the holding time at the holding temperature should be in the range of 5 minutes or more and 180 minutes or less.
- the holding temperature is more preferably less than 200°C.
- the alcohol reduces the copper complex to generate nano-sized copper particles, and the organic components (acid component of the copper salt, amine, alcohol) volatilize, of the liquid phase 21 disappears.
- the bonding metal paste 20 contains a silver salt, the silver complex formed by the silver salt and the amine is reduced with alcohol to generate nano-sized silver particles.
- the heating temperature is set to a temperature higher than the liquid phase disappearance temperature.
- the heating temperature is preferably in the range of 200° C. or more and 400° C. or less, and the holding time at the heating temperature is preferably in the range of 1 minute or more and 90 minutes or less.
- sintering of the metal powder proceeds, and as shown in FIG.
- the metal paste for bonding 20 contains a silver salt, sintering proceeds sufficiently by generating nano-sized silver particles, and it is possible to improve the bonding strength.
- the bonding metal paste of the present embodiment configured as described above, it contains metal powder, copper salt, amine, and alcohol, and is in the form of a paste within a temperature range of 15° C. or higher and 35° C. or lower, Since a liquid phase is generated in the process of raising the temperature from 35° C., when the metal paste 20 for bonding is disposed between the first member 11 and the second member 12 for bonding, A liquid phase is generated between the first member 11 and the second member 12 in the temperature rising process during bonding, and the surface tension of this liquid phase causes the relative positions of the first member 11 and the second member 12 to be self-aligned. can do. In addition, since the metal powder is contained, even if a liquid phase occurs, a distance can be secured between the first member 11 and the second member 12, and the bonding layer 15 can be sufficiently formed. .
- the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body.
- a bonding layer having excellent heat resistance and bonding strength can be formed without generating a liquid phase even when placed in a high-temperature environment later.
- the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is set within a range of 0.02 or more, so that the content of the copper salt is ensured, A sufficient liquid phase is formed in the temperature rising process during bonding, and self-alignment can be achieved.
- the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is within the range of 0.25 or less, the amount of the liquid phase generated does not become excessive, and the volatile organic matter By suppressing the amount, the density of the metal sintered body after firing becomes sufficiently high, and high bonding strength can be realized. Furthermore, in the present embodiment, since alcohol is included, nano-sized copper particles can be generated by reducing the copper ions of the copper salt that has become a liquid phase in the process of increasing the temperature during bonding. The organic component complexed with copper ions is volatilized, and the liquid phase can be reliably eliminated.
- the bonding layer 15 made of a sintered body of these metals can be formed. It is possible to form the bonding layer 15 that is particularly excellent in heat conduction.
- the metal complex when the copper salt contains an organic carboxylic acid copper salt, the metal complex can be reliably formed by adding it together with the amine. A liquid phase can be made to appear reliably.
- the mixture becomes a paste in the temperature range of 15° C. or higher and 35° C. or lower with a single copper salt. Even if not, it is possible to make the mixture into a paste in a temperature range of 15° C. or more and 35° C. or less by combining two or more kinds. Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
- the metal complex when the amine contains a linear alkylamine, the metal complex can be reliably formed by adding it together with the copper salt, and the metal complex can be reliably formed during the temperature rising process during bonding.
- a liquid phase can appear at
- the mixture when two or more kinds of amines are included as amines, the mixture does not become a paste in the temperature range of 15° C. or more and 35° C. or less with single amines. Also, by combining two or more kinds, it is possible to make the mixture into a paste in a temperature range of 15° C. or more and 35° C. or less. Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
- the metal paste for bonding of the present embodiment when two or more types of alcohol are included as the alcohol, even if the paste viscosity is not optimal depending on the method of use with the single alcohol, it is possible to combine two or more types of alcohol. makes it possible to adjust the paste viscosity to a suitable value.
- the metal paste for bonding of the present embodiment contains a silver salt in addition to the metal powder, copper salt, amine, and alcohol, the silver salt reacts with the amine to form a silver complex, Since nano-sized silver particles are generated by reducing the silver complex with alcohol, it is possible to further improve the bonding strength.
- the joining metal paste 20 is disposed between the first member 11 and the second member 12 in the temperature range of 15° C. or higher and 35° C. or lower, and then Since the liquid phase 21 is generated by raising the temperature, the relative positions of the first member 11 and the second member 12 can be self-aligned by the surface tension of the liquid phase 21 . Further, in the present embodiment, the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body. It is possible to form the bonding layer 15 composed of the above, and to manufacture the bonded body 10 having excellent heat resistance and bonding strength.
- the present invention is not limited to this, and can be modified as appropriate without departing from the technical idea of the invention.
- the circuit layer (first member) of the insulated circuit board is described as being joined with a semiconductor element (second member) as an electronic component. It is sufficient that the member and the second member are joined using the joining metal paste of the present invention.
- Example 1 First, copper salts and amines shown in Tables 1 and 2 were mixed at the ratios shown in Tables 1 and 2 to obtain copper salt-amine mixtures. Then, the copper salt-amine mixture was mixed with the metal powder and alcohol shown in Tables 1 and 2 to obtain various mixtures according to Inventive Examples 1-19 and Comparative Examples 1-15.
- Tables 1 and 2 the metal particle size of the metal powder used is shown in parentheses.
- Sn-3.0% Ag-0.5% Cu cream solder manufactured by Senju Metal Industry Co., Ltd.
- Comparative Example 12 the Cu core Sn shell paste described in Example 1 of Japanese Patent No. 6645317 was used.
- Example 1-19 and Comparative Examples 9, 10, 13, and 14 of the present invention the temperature was raised from room temperature, held at the liquid phase volatilization process temperature shown in Tables 3 and 4 for 60 minutes, and further heated. Then, the temperature in the firing process shown in Tables 3 and 4 was maintained for 15 minutes, and then the temperature was lowered to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 2° C./min.
- Comparative Example 11 using SnAgCu as the metal powder the temperature was raised from room temperature, held at the liquid phase volatilization process temperature shown in Table 4 for 3 minutes, and further heated to 10 minutes at the firing process temperature shown in Table 4. The temperature was maintained for a second and then cooled to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 30° C./min. Also, the melting temperature of SnAgCu was taken as the liquid phase formation temperature, and the volatilization temperature of the flux was taken as the liquid phase disappearance temperature.
- Comparative Example 12 using a Cu core and Sn shell as the metal powder, the temperature was raised from room temperature, the liquid phase volatilization process temperature shown in Table 4 was maintained for 3 minutes, and the temperature was further raised to perform the firing process shown in Table 4. The temperature was held for 10 seconds and then cooled to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 30° C./min. Also, the melting point of Sn was taken as the liquid phase formation temperature, and the volatilization temperature of the flux was taken as the liquid phase disappearance temperature.
- the liquid phase formation temperature was the temperature at the point where the tangent line drawn from the peak of the DTA curve toward the low temperature portion (low temperature side) intersects with the extended line of the flat portion of the DTA curve, as shown in FIG.
- the bonding strength was measured using a shear strength evaluation tester (MFM 1500HF manufactured by TRY PRESICION). Specifically, the bonding strength was measured by fixing the oxygen-free copper plate of the bonded body horizontally, and moving the Si chip of the bonded body horizontally from the side with a shear tool at a position 50 ⁇ m above the surface (upper surface) of the bonding layer. , and measured the strength when the Si chip was broken. In addition, the moving speed of the share tool was set to 0.1 mm/sec. The strength test was performed three times per condition, and the arithmetic mean value thereof was used as the measurement value of the bonding strength.
- the sample after firing was heated at 175°C for 15 minutes using a thermal shock tester (TSE-11-A manufactured by Espec Co., Ltd.), cooled to -40°C for 15 minutes, and then heated to 175°C.
- a thermal shock test was conducted for 100 cycles, in which one cycle is the process of Using an ultrasonic imaging device (FSP8V manufactured by Hitachi Power Solutions Co., Ltd.), an image was taken to confirm the portion where the oxygen-free copper plate and the Si chip were bonded by the bonding layer.
- the transducer (probe) used has a frequency of 140 MHz.
- the peeled area was determined from the photographed image, and "A” was given when the peeled area was less than 10% of the chip area, and "B” was given when it was 10% or more.
- the image obtained by the ultrasonic imaging device the part where the Si chip and the oxygen-free copper plate are peeled off looks white, and the part where they are joined looks gray.
- Comparative Examples 1, 2, and 4-6 the mixture was powdery in the temperature range of 15° C. or higher and 35° C. or lower, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
- Comparative Examples 3, 7, 8, and 15 the mixture was liquid in the temperature range of 15° C. or more and 35° C. or less, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
- Comparative Examples 11 and 12 Cu—Sn based solder materials were used, and the heat resistance was insufficient.
- Comparative Example 13 an Ag paste containing no copper salt was used, and no liquid phase was generated during the temperature rising process, resulting in self-alignment of "B".
- Comparative Example 14 the firing process temperature was lower than the liquid phase disappearance temperature, organic components remained inside the bonding layer made of the sintered metal, and the bonding strength was low.
- Inventive Example 1-19 contains a metal powder, a copper salt and an amine, is in a paste form within the temperature range of 15° C. or higher and 35° C. or lower, and becomes liquid in the process of raising the temperature from 35° C. A phase is generated, and the liquid phase disappears in the process of raising the temperature above the liquid phase generation temperature, and the metal sintered body is formed at the liquid phase disappearance temperature or higher. It was excellent in durability and bonding strength.
- a liquid phase is generated in the temperature rising process at the time of bonding, and the relative positions of the members can be adjusted by self-alignment, and heat resistance and bonding strength can be improved. It was confirmed that it is possible to provide a bonding metal paste capable of forming an excellent bonding layer and a method for manufacturing a bonded body.
- Example 2 Inventive Example 20 was obtained by adding 4 mass % of a silver salt (silver acetate) to the joining metal paste of Inventive Example 2 shown in Table 1. Next, an oxygen-free copper plate having a thickness of 2 mm whose outermost surface was metallized with Ag (hereinafter referred to as Ag-metallized copper plate) was prepared.
- a silver salt silver acetate
- Ag-metallized copper plate an oxygen-free copper plate having a thickness of 2 mm whose outermost surface was metallized with Ag
- the bonding metal pastes of Inventive Example 2 and Inventive Example 20 were arranged (thickness: 100 ⁇ m, area: 3 mm square).
- a square Si chip with a thickness of 2.5 mm and a side of 2.5 mm (Au-metallized surface) was mounted on the provided mixture. This was heated to form a bonding layer, and the oxygen-free copper plate and the Si chip were bonded together.
- the conditions shown in Table 5 were set for the heating temperature and holding time in the liquid phase volatilization step, and the heating temperature and holding time in the firing step. Then, the shear strength was measured in the same procedure as in Example 1. Table 5 shows the measurement results.
- the metal paste for bonding of Inventive Example 20 to which a silver salt is added has an improved shear strength compared to the metal paste for bonding of Inventive Example 2 to which no silver salt is added. was confirmed.
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Abstract
This metal paste for joining includes a metal powder, a copper salt, an amine, and an alcohol, the ratio A/B of the weight A of Cu in the copper salt and the weight B of the metal powder is placed in the range of 0.02 to 0.25, the metal paste is in the form of a paste in the temperature range of 15-35°C, a liquid phase occurs over the course of increasing the temperature from 35°C, the liquid phase dissipates over the course of increasing the temperature above the liquid phase generation temperature, and a metal sintered compact is formed at or above the liquid phase dissipation temperature.
Description
本発明は、部材同士を接合する際に用いられる接合用金属ペースト、および、この接合用金属ペーストを用いた接合体の製造方法に関する。
本願は、２０２１年４月１日に、日本に出願された特願２０２１－０６２７７０号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a bonding metal paste used for bonding members together, and a method for manufacturing a bonded body using this bonding metal paste.
This application claims priority based on Japanese Patent Application No. 2021-062770 filed in Japan on April 1, 2021, the content of which is incorporated herein.
本願は、２０２１年４月１日に、日本に出願された特願２０２１－０６２７７０号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a bonding metal paste used for bonding members together, and a method for manufacturing a bonded body using this bonding metal paste.
This application claims priority based on Japanese Patent Application No. 2021-062770 filed in Japan on April 1, 2021, the content of which is incorporated herein.
例えば、ＬＥＤやパワーモジュールといった半導体装置は、金属部材からなる回路層の上に半導体素子が接合された構造とされている。
ここで、半導体素子等の電子部品を回路層上に接合する際には、例えば特許文献１に示すように、はんだ材を用いた方法が広く使用されている。
また、特許文献２には、めっき膜とＳｎ系はんだ層を形成し、熱処理によってこれらを合金化して合金層を形成し、電子部品を基板に実装する技術が提案されている。 For example, semiconductor devices such as LEDs and power modules have a structure in which a semiconductor element is bonded onto a circuit layer made of a metal member.
Here, when an electronic component such as a semiconductor element is joined onto a circuit layer, a method using a solder material is widely used as disclosed inPatent Document 1, for example.
Further, Patent Document 2 proposes a technique of forming a plating film and a Sn-based solder layer, alloying them by heat treatment to form an alloy layer, and mounting an electronic component on a substrate.
ここで、半導体素子等の電子部品を回路層上に接合する際には、例えば特許文献１に示すように、はんだ材を用いた方法が広く使用されている。
また、特許文献２には、めっき膜とＳｎ系はんだ層を形成し、熱処理によってこれらを合金化して合金層を形成し、電子部品を基板に実装する技術が提案されている。 For example, semiconductor devices such as LEDs and power modules have a structure in which a semiconductor element is bonded onto a circuit layer made of a metal member.
Here, when an electronic component such as a semiconductor element is joined onto a circuit layer, a method using a solder material is widely used as disclosed in
Further, Patent Document 2 proposes a technique of forming a plating film and a Sn-based solder layer, alloying them by heat treatment to form an alloy layer, and mounting an electronic component on a substrate.
さらに、特許文献３には、金属粉を有する金属ペーストを用いて、半導体素子等の電子部品を回路上に接合する技術が提案されている。この金属ペーストにおいては、導電性の焼結体からなる接合層が形成され、この接合層を介して半導体素子等の電子部品が回路上に接合されることになる。
Furthermore, Patent Document 3 proposes a technique for bonding electronic components such as semiconductor elements onto a circuit using a metal paste containing metal powder. In this metal paste, a bonding layer made of a conductive sintered body is formed, and an electronic component such as a semiconductor element is bonded to a circuit via this bonding layer.
ところで、特許文献１，２に記載されたように、はんだ材を用いて、部材同士を接合する際には、接合時の昇温過程において液相が生じる。このとき、液相の表面張力によって部材同士の相対位置が調整される。すなわち、部材同士の相対位置がセルフアライメントされることになる。
しかしながら、はんだ材を用いて接合した場合には、部材同士の間に形成される接合層には、金属間化合物が生成しており、熱伝導率が比較的低くなるおそれがあった。さらに、温度サイクルを負荷した際に接合層にクラックが生じ易く、接合信頼性が低下するおそれがあった。 By the way, as described inPatent Documents 1 and 2, when members are joined together using a solder material, a liquid phase is generated in the temperature rising process during joining. At this time, the relative positions of the members are adjusted by the surface tension of the liquid phase. That is, the relative positions of the members are self-aligned.
However, when the members are joined using a solder material, an intermetallic compound is formed in the joining layer formed between the members, and there is a possibility that the thermal conductivity becomes relatively low. Furthermore, when a temperature cycle is applied, cracks are likely to occur in the bonding layer, and there is a possibility that the reliability of the bonding may be lowered.
しかしながら、はんだ材を用いて接合した場合には、部材同士の間に形成される接合層には、金属間化合物が生成しており、熱伝導率が比較的低くなるおそれがあった。さらに、温度サイクルを負荷した際に接合層にクラックが生じ易く、接合信頼性が低下するおそれがあった。 By the way, as described in
However, when the members are joined using a solder material, an intermetallic compound is formed in the joining layer formed between the members, and there is a possibility that the thermal conductivity becomes relatively low. Furthermore, when a temperature cycle is applied, cracks are likely to occur in the bonding layer, and there is a possibility that the reliability of the bonding may be lowered.
さらに、はんだ材を介して半導体素子等の電子部品と回路層とを接合した場合には、高温環境下で使用した際にはんだの一部が溶融し、半導体素子等の電子部品と回路層と接合信頼性が低下するおそれがあった。
特に、最近では、半導体素子自体の耐熱性が向上しており、かつ、半導体装置が自動車のエンジンルーム等の高温環境下で使用されることがあり、従来のようにはんだ材で接合した構造では対応が困難となってきている。 Furthermore, when an electronic component such as a semiconductor element and a circuit layer are joined via a solder material, part of the solder melts when used in a high-temperature environment, resulting in There was a possibility that the bonding reliability would be degraded.
In particular, in recent years, the heat resistance of semiconductor elements themselves has improved, and semiconductor devices are sometimes used in high-temperature environments such as automobile engine compartments. It is becoming difficult to respond.
特に、最近では、半導体素子自体の耐熱性が向上しており、かつ、半導体装置が自動車のエンジンルーム等の高温環境下で使用されることがあり、従来のようにはんだ材で接合した構造では対応が困難となってきている。 Furthermore, when an electronic component such as a semiconductor element and a circuit layer are joined via a solder material, part of the solder melts when used in a high-temperature environment, resulting in There was a possibility that the bonding reliability would be degraded.
In particular, in recent years, the heat resistance of semiconductor elements themselves has improved, and semiconductor devices are sometimes used in high-temperature environments such as automobile engine compartments. It is becoming difficult to respond.
一方、特許文献３に記載された金属ペーストにおいては、接合層が金属の焼結体で構成されていることから、熱伝導率に優れており、接合信頼性にも優れている。
また、金属の焼結体によって接合層を形成した場合には、比較的低温条件で接合層を形成できるとともに接合層自体の融点は高くなるため、高温環境下においても接合強度が大きく低下しない。
しかしながら、金属ペーストを用いて部材同士を接合する場合には、接合時の昇温過程において液相が生じない。このため、部材同士の相対位置をセルフアライメントすることができなかった。 On the other hand, in the metal paste described in Patent Document 3, since the bonding layer is composed of a metal sintered body, it has excellent thermal conductivity and excellent bonding reliability.
In addition, when the bonding layer is formed of a sintered metal, the bonding layer can be formed under relatively low temperature conditions and the melting point of the bonding layer itself is high, so that the bonding strength does not significantly decrease even in a high temperature environment.
However, when joining members using a metal paste, a liquid phase does not occur in the temperature rising process during joining. Therefore, self-alignment of the relative positions of the members could not be achieved.
また、金属の焼結体によって接合層を形成した場合には、比較的低温条件で接合層を形成できるとともに接合層自体の融点は高くなるため、高温環境下においても接合強度が大きく低下しない。
しかしながら、金属ペーストを用いて部材同士を接合する場合には、接合時の昇温過程において液相が生じない。このため、部材同士の相対位置をセルフアライメントすることができなかった。 On the other hand, in the metal paste described in Patent Document 3, since the bonding layer is composed of a metal sintered body, it has excellent thermal conductivity and excellent bonding reliability.
In addition, when the bonding layer is formed of a sintered metal, the bonding layer can be formed under relatively low temperature conditions and the melting point of the bonding layer itself is high, so that the bonding strength does not significantly decrease even in a high temperature environment.
However, when joining members using a metal paste, a liquid phase does not occur in the temperature rising process during joining. Therefore, self-alignment of the relative positions of the members could not be achieved.
この発明は、前述した事情に鑑みてなされたものであって、接合時の昇温過程において液相を生じさせ、セルフアライメントによって部材同士の相対位置の位置調整を行うことができ、かつ、耐熱性、接合強度に優れた金属焼結体からなる接合層を形成可能な接合用金属ペースト、および、この接合用金属ペーストを用いた接合体の製造方法を提供することを目的とする。
The present invention has been made in view of the above-mentioned circumstances, and is capable of generating a liquid phase in the temperature rising process during bonding, adjusting the relative positions of members by self-alignment, and providing a heat-resistant member. It is an object of the present invention to provide a bonding metal paste capable of forming a bonding layer composed of a metal sintered body with excellent bonding strength and bonding strength, and a method for manufacturing a bonded body using this bonding metal paste.
上記課題を解決するために、本発明の接合用金属ペーストは、金属粉と銅塩とアミンとアルコールとを含み、前記銅塩中のＣｕ重量Ａと前記金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされており、１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相が生成し、液相生成温度以上の昇温過程で液相が消失し、液相消失温度以上で金属焼結体を形成することを特徴としている。
In order to solve the above problems, the metal paste for bonding of the present invention contains a metal powder, a copper salt, an amine, and an alcohol, and the ratio of the weight A of Cu in the copper salt to the weight B of the metal powder is A/ B is in the range of 0.02 or more and 0.25 or less, it is pasty within the temperature range of 15 ° C. or more and 35 ° C. or less, and a liquid phase is generated in the process of raising the temperature from 35 ° C., and the liquid phase It is characterized in that the liquid phase disappears in the process of increasing the temperature above the production temperature, and a metal sintered body is formed above the liquid phase disappearance temperature.
この構成の接合用金属ペーストによれば、金属粉と銅塩とアミンとアルコールとを含み、１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相を生成する構成とされているので、室温での作業環境においては印刷またはディスペンス塗布またはピン転写が可能である。一方、接合時の昇温過程では液相が生じ、接合部材同士の相対位置をセルフアライメントすることができる。なお、金属粉を含有しているので、液相が生じた場合でも、部材同士の間に距離を確保することができ、接合層を十分に形成することができる。
さらに、液相生成温度以上で液相が消失し、液相消失温度以上で金属焼結体を形成する構成とされているので、高温環境下でも接合強度が低下せず、耐熱性、接合強度に優れた接合層を形成することができる。
また、前記銅塩中のＣｕ重量Ａと前記金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされているので、昇温過程で液相を十分に形成することができるとともに、焼成後の金属焼結体密度が十分高くなり強い接合強度を実現できる。
さらに、アルコールを含んでいるので、接合時の昇温過程において、液相となった銅塩の銅イオンを還元することでナノサイズの銅粒子を生成することができ、銅イオンと錯形成していた有機成分が揮発するようになり液相を確実に消失させることが可能となる。 According to the bonding metal paste having this configuration, the metal powder, the copper salt, the amine, and the alcohol are included, the paste is in the form of a paste within the temperature range of 15° C. or higher and 35° C. or lower, and the liquid phase is formed in the process of increasing the temperature from 35° C. can be printed or dispensed or pin-transferred in a working environment at room temperature. On the other hand, a liquid phase is generated in the temperature rising process during bonding, and the relative positions of the bonding members can be self-aligned. In addition, since the metal powder is contained, even if a liquid phase occurs, a distance can be secured between the members, and a sufficient bonding layer can be formed.
Furthermore, the liquid phase disappears at the liquid phase generation temperature or higher, and the metal sintered body is formed at the liquid phase disappearance temperature or higher, so the bonding strength does not decrease even in a high temperature environment. It is possible to form a bonding layer excellent in
Further, since the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less, the liquid phase is sufficiently In addition, the density of the metal sintered body after sintering becomes sufficiently high, and strong bonding strength can be realized.
Furthermore, since it contains alcohol, it is possible to generate nano-sized copper particles by reducing the copper ions of the copper salt that has become a liquid phase in the process of increasing the temperature during bonding, and form a complex with the copper ions. The organic component that had been in the liquid phase becomes volatilized, and the liquid phase can be reliably eliminated.
さらに、液相生成温度以上で液相が消失し、液相消失温度以上で金属焼結体を形成する構成とされているので、高温環境下でも接合強度が低下せず、耐熱性、接合強度に優れた接合層を形成することができる。
また、前記銅塩中のＣｕ重量Ａと前記金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされているので、昇温過程で液相を十分に形成することができるとともに、焼成後の金属焼結体密度が十分高くなり強い接合強度を実現できる。
さらに、アルコールを含んでいるので、接合時の昇温過程において、液相となった銅塩の銅イオンを還元することでナノサイズの銅粒子を生成することができ、銅イオンと錯形成していた有機成分が揮発するようになり液相を確実に消失させることが可能となる。 According to the bonding metal paste having this configuration, the metal powder, the copper salt, the amine, and the alcohol are included, the paste is in the form of a paste within the temperature range of 15° C. or higher and 35° C. or lower, and the liquid phase is formed in the process of increasing the temperature from 35° C. can be printed or dispensed or pin-transferred in a working environment at room temperature. On the other hand, a liquid phase is generated in the temperature rising process during bonding, and the relative positions of the bonding members can be self-aligned. In addition, since the metal powder is contained, even if a liquid phase occurs, a distance can be secured between the members, and a sufficient bonding layer can be formed.
Furthermore, the liquid phase disappears at the liquid phase generation temperature or higher, and the metal sintered body is formed at the liquid phase disappearance temperature or higher, so the bonding strength does not decrease even in a high temperature environment. It is possible to form a bonding layer excellent in
Further, since the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less, the liquid phase is sufficiently In addition, the density of the metal sintered body after sintering becomes sufficiently high, and strong bonding strength can be realized.
Furthermore, since it contains alcohol, it is possible to generate nano-sized copper particles by reducing the copper ions of the copper salt that has become a liquid phase in the process of increasing the temperature during bonding, and form a complex with the copper ions. The organic component that had been in the liquid phase becomes volatilized, and the liquid phase can be reliably eliminated.
また、本発明の接合用金属ペーストにおいては、前記金属粉は、銀、銅のいずれか一種または二種であることが好ましい。
この場合、金属粉が、銀、銅のいずれか一種または二種とされているので、熱伝導に特に優れた接合層を形成することが可能となる。 Moreover, in the metal paste for bonding of the present invention, the metal powder is preferably one or two of silver and copper.
In this case, since the metal powder is one or two of silver and copper, it is possible to form a bonding layer that is particularly excellent in heat conduction.
この場合、金属粉が、銀、銅のいずれか一種または二種とされているので、熱伝導に特に優れた接合層を形成することが可能となる。 Moreover, in the metal paste for bonding of the present invention, the metal powder is preferably one or two of silver and copper.
In this case, since the metal powder is one or two of silver and copper, it is possible to form a bonding layer that is particularly excellent in heat conduction.
さらに、本発明の接合用金属ペーストにおいては、前記銅塩は、有機カルボン酸銅塩を含むことが好ましい。
この場合、前記銅塩が有機カルボン酸銅塩を含むものとされているので、アミンとともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。 Furthermore, in the metal paste for bonding of the present invention, the copper salt preferably contains an organic carboxylic acid copper salt.
In this case, since the copper salt contains an organic carboxylic acid copper salt, the metal complex can be reliably formed by adding it together with the amine, and the liquid phase can be reliably formed during the temperature rising process during bonding. can appear.
この場合、前記銅塩が有機カルボン酸銅塩を含むものとされているので、アミンとともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。 Furthermore, in the metal paste for bonding of the present invention, the copper salt preferably contains an organic carboxylic acid copper salt.
In this case, since the copper salt contains an organic carboxylic acid copper salt, the metal complex can be reliably formed by adding it together with the amine, and the liquid phase can be reliably formed during the temperature rising process during bonding. can appear.
さらに、本発明の接合用金属ペーストにおいては、前記銅塩は２種類以上含まれていても良い。
この場合、単体の銅塩では１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。 Furthermore, the metal paste for bonding of the present invention may contain two or more of the copper salts.
In this case, even if a single copper salt does not form a paste at a temperature range of 15°C or higher and 35°C or lower, a combination of two or more kinds of the copper salt can form a paste at a temperature range of 15°C or higher and 35°C or lower. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
この場合、単体の銅塩では１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。 Furthermore, the metal paste for bonding of the present invention may contain two or more of the copper salts.
In this case, even if a single copper salt does not form a paste at a temperature range of 15°C or higher and 35°C or lower, a combination of two or more kinds of the copper salt can form a paste at a temperature range of 15°C or higher and 35°C or lower. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
また、本発明の接合用金属ペーストにおいては、前記アミンが直鎖アルキルアミンを含むことが好ましい。
この場合、前記アミンが直鎖アルキルアミンを含むものとされているので、銅塩とともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。 Moreover, in the metal paste for joining of this invention, it is preferable that the said amine contains a linear alkylamine.
In this case, since the amine is supposed to contain a straight-chain alkylamine, it is possible to reliably form a metal complex by adding it together with a copper salt, and a liquid phase reliably appears during the heating process during bonding. can be made
この場合、前記アミンが直鎖アルキルアミンを含むものとされているので、銅塩とともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。 Moreover, in the metal paste for joining of this invention, it is preferable that the said amine contains a linear alkylamine.
In this case, since the amine is supposed to contain a straight-chain alkylamine, it is possible to reliably form a metal complex by adding it together with a copper salt, and a liquid phase reliably appears during the heating process during bonding. can be made
また、本発明の接合用金属ペーストにおいては、前記アミンが２種類以上のアミンから成るものとしても良い。
この場合、単体のアミンでは１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。 Moreover, in the metal paste for bonding of the present invention, the amine may be composed of two or more kinds of amines.
In this case, even if a single amine does not form a paste in a temperature range of 15°C to 35°C, a mixture of two or more amines can be combined to form a paste in a temperature range of 15°C to 35°C. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
この場合、単体のアミンでは１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。 Moreover, in the metal paste for bonding of the present invention, the amine may be composed of two or more kinds of amines.
In this case, even if a single amine does not form a paste in a temperature range of 15°C to 35°C, a mixture of two or more amines can be combined to form a paste in a temperature range of 15°C to 35°C. It becomes possible to Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
また、本発明の接合用金属ペーストにおいては、前記アルコールが２種類以上のアルコールから成るものとしいても良い。
この場合、単体のアルコールではペースト粘度が使用方法によっては最適でないものであっても、２種類以上組み合わせることによってペースト粘度を適した値に調整することが可能となる。 In addition, in the metal paste for bonding of the present invention, the alcohol may consist of two or more alcohols.
In this case, even if the paste viscosity is not optimal for a single alcohol depending on the method of use, it is possible to adjust the paste viscosity to a suitable value by combining two or more alcohols.
この場合、単体のアルコールではペースト粘度が使用方法によっては最適でないものであっても、２種類以上組み合わせることによってペースト粘度を適した値に調整することが可能となる。 In addition, in the metal paste for bonding of the present invention, the alcohol may consist of two or more alcohols.
In this case, even if the paste viscosity is not optimal for a single alcohol depending on the method of use, it is possible to adjust the paste viscosity to a suitable value by combining two or more alcohols.
また、本発明の接合用金属ペーストにおいては、金属粉と銅塩とアミンとアルコールに加えて、さらに銀塩を含んでいることが好ましい。
この場合、銀塩がアミンと反応して銀錯体を形成し、この銀錯体をアルコールが還元することでナノサイズの銀粒子が生成することから、接合強度のさらなる向上を図ることが可能となる。 Moreover, the metal paste for bonding of the present invention preferably contains a silver salt in addition to the metal powder, copper salt, amine and alcohol.
In this case, the silver salt reacts with the amine to form a silver complex, and the silver complex is reduced by alcohol to generate nano-sized silver particles, making it possible to further improve the bonding strength. .
この場合、銀塩がアミンと反応して銀錯体を形成し、この銀錯体をアルコールが還元することでナノサイズの銀粒子が生成することから、接合強度のさらなる向上を図ることが可能となる。 Moreover, the metal paste for bonding of the present invention preferably contains a silver salt in addition to the metal powder, copper salt, amine and alcohol.
In this case, the silver salt reacts with the amine to form a silver complex, and the silver complex is reduced by alcohol to generate nano-sized silver particles, making it possible to further improve the bonding strength. .
本発明の接合体の製造方法は、第１部材と第２部材とが接合された接合体の製造方法であって、１５℃以上３５℃以下の温度範囲で、前記第１部材と前記第２部材との間に、上述の接合用金属ペーストを配設し、前記第１部材と前記第２部材との間に前記接合用金属ペーストを配設した状態で昇温して、前記第１部材と前記第２部材との間に液相を生じさせ、さらに液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成し、前記第１部材と前記第２部材とを接合することを特徴としている。
A method for manufacturing a bonded body of the present invention is a method for manufacturing a bonded body in which a first member and a second member are bonded, wherein the first member and the second member are The above-described bonding metal paste is disposed between the first member and the second member, and the temperature is raised in a state where the bonding metal paste is disposed between the first member and the second member. and the second member, the temperature is raised to the liquid phase generation temperature or higher to disappear the liquid phase, and the temperature is further raised to the liquid phase disappearance temperature or higher to form a metal sintered body. and joining the first member and the second member.
この構成の接合体の製造方法によれば、１５℃以上３５℃以下の温度範囲で前記第１部材と前記第２部材との間に上述の接合用金属ペーストを配設し、その後、昇温して液相を生じさせているので、液相の表面張力によって、第１部材と第２部材との相対位置をセルフアライメントすることができる。
また、液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成しているので、金属焼結体からなる接合層を形成でき、耐熱性、接合強度に優れた接合体を製造することができる。 According to the method for manufacturing a bonded body having this configuration, the metal paste for bonding is disposed between the first member and the second member in a temperature range of 15° C. or higher and 35° C. or lower, and then the temperature is raised. Since the surface tension of the liquid phase causes self-alignment of the relative positions of the first member and the second member.
In addition, since the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body, a bonding layer made of the metal sintered body is formed. It is possible to manufacture a bonded body excellent in heat resistance and bonding strength.
また、液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成しているので、金属焼結体からなる接合層を形成でき、耐熱性、接合強度に優れた接合体を製造することができる。 According to the method for manufacturing a bonded body having this configuration, the metal paste for bonding is disposed between the first member and the second member in a temperature range of 15° C. or higher and 35° C. or lower, and then the temperature is raised. Since the surface tension of the liquid phase causes self-alignment of the relative positions of the first member and the second member.
In addition, since the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body, a bonding layer made of the metal sintered body is formed. It is possible to manufacture a bonded body excellent in heat resistance and bonding strength.
本発明によれば、接合時の昇温過程において液相を生じさせ、セルフアライメントによって部材同士の相対位置の位置調整を行うことができ、かつ、耐熱性、接合強度に優れた金属焼結体からなる接合層を形成可能な接合用金属ペースト、および、この接合用金属ペーストを用いた接合体の製造方法を提供することができる。
According to the present invention, a metal sintered body that generates a liquid phase in the temperature rising process during bonding, can adjust the relative position of members by self-alignment, and has excellent heat resistance and bonding strength. It is possible to provide a bonding metal paste capable of forming a bonding layer composed of the above metal bonding paste, and a method for manufacturing a bonded body using this bonding metal paste.
以下に、本発明の一実施形態に係る接合用金属ペースト、および、接合体の製造方法について説明する。
本実施形態の接合用金属ペーストは、第１部材と第２部材とを接合して接合体を製造する際に使用されるものである。例えば、絶縁回路基板の回路層（第１部材）に、電子部品として半導体素子（第２部材）を接合する際に用いられるものである。 A metal paste for bonding and a method for manufacturing a bonded body according to an embodiment of the present invention will be described below.
The metal paste for bonding of the present embodiment is used when manufacturing a bonded body by bonding the first member and the second member. For example, it is used when bonding a semiconductor element (second member) as an electronic component to a circuit layer (first member) of an insulated circuit board.
本実施形態の接合用金属ペーストは、第１部材と第２部材とを接合して接合体を製造する際に使用されるものである。例えば、絶縁回路基板の回路層（第１部材）に、電子部品として半導体素子（第２部材）を接合する際に用いられるものである。 A metal paste for bonding and a method for manufacturing a bonded body according to an embodiment of the present invention will be described below.
The metal paste for bonding of the present embodiment is used when manufacturing a bonded body by bonding the first member and the second member. For example, it is used when bonding a semiconductor element (second member) as an electronic component to a circuit layer (first member) of an insulated circuit board.
本実施形態の接合用金属ペーストは、金属粉と銅塩とアミンとアルコールとを含んでいる。さらに、本実施形態の接合用金属ペーストは、銀塩を含有してもよい。
また、本実施形態の接合用金属ペーストにおいては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされている。 The bonding metal paste of the present embodiment contains metal powder, copper salt, amine, and alcohol. Furthermore, the metal paste for joining of this embodiment may contain a silver salt.
In addition, in the metal paste for bonding of the present embodiment, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less.
また、本実施形態の接合用金属ペーストにおいては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされている。 The bonding metal paste of the present embodiment contains metal powder, copper salt, amine, and alcohol. Furthermore, the metal paste for joining of this embodiment may contain a silver salt.
In addition, in the metal paste for bonding of the present embodiment, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less.
そして、本実施形態のる接合用金属ペーストにおいては、１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相が生成し、液相生成温度以上で液相が消失し、液相消失温度以上で金属焼結体を形成する構成とされている。
The metal paste for bonding according to the present embodiment is paste-like within a temperature range of 15° C. or higher and 35° C. or lower. The liquid phase disappears and the metal sintered body is formed at a temperature equal to or higher than the liquid phase disappearance temperature.
本実施形態においては、上述のように、接合用金属ペーストが銅塩とアミンとを含んでいることから、これらを混合することで金属錯体（銅錯体）が形成されることになる。この金属錯体は、１５℃以上３５℃以下の温度範囲内でペースト状となり、さらに加熱することで液相が生じることになる。
In the present embodiment, as described above, the metal paste for bonding contains a copper salt and an amine, so that a metal complex (copper complex) is formed by mixing these. This metal complex becomes a paste within a temperature range of 15° C. or higher and 35° C. or lower, and a liquid phase is generated by further heating.
ここで、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０２未満の場合には、銅塩の含有量が不十分となり、接合時の昇温過程で液相が十分に形成されずセルフアライメント性が損なわれるおそれがある。一方、上述の重量比Ａ／Ｂが０．２５を超えると、液相が過剰に生成し、揮発する有機物量が多くなり、焼成後の金属焼結体密度が低くなり接合強度が低くなるおそれがある。
このことから、本実施形態では、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂを０．０２以上０．２５以下の範囲内に設定している。
なお、上述の重量比Ａ／Ｂは、０．０４以上であることが好ましく、０．０６以上であることがさらに好ましい。また、上述の重量比Ａ／Ｂは、０．２０以下であることが好ましく、０．１５以下であることがさらに好ましい。 Here, when the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is less than 0.02, the content of the copper salt becomes insufficient and the liquid is There is a risk that the phase will not be sufficiently formed and the self-alignment property will be impaired. On the other hand, if the weight ratio A/B exceeds 0.25, the liquid phase is excessively generated, the amount of volatilized organic matter increases, the density of the metal sintered body after firing decreases, and the bonding strength may decrease. There is
For this reason, in the present embodiment, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is set within the range of 0.02 or more and 0.25 or less.
The above weight ratio A/B is preferably 0.04 or more, more preferably 0.06 or more. Also, the above weight ratio A/B is preferably 0.20 or less, more preferably 0.15 or less.
このことから、本実施形態では、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂを０．０２以上０．２５以下の範囲内に設定している。
なお、上述の重量比Ａ／Ｂは、０．０４以上であることが好ましく、０．０６以上であることがさらに好ましい。また、上述の重量比Ａ／Ｂは、０．２０以下であることが好ましく、０．１５以下であることがさらに好ましい。 Here, when the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is less than 0.02, the content of the copper salt becomes insufficient and the liquid is There is a risk that the phase will not be sufficiently formed and the self-alignment property will be impaired. On the other hand, if the weight ratio A/B exceeds 0.25, the liquid phase is excessively generated, the amount of volatilized organic matter increases, the density of the metal sintered body after firing decreases, and the bonding strength may decrease. There is
For this reason, in the present embodiment, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is set within the range of 0.02 or more and 0.25 or less.
The above weight ratio A/B is preferably 0.04 or more, more preferably 0.06 or more. Also, the above weight ratio A/B is preferably 0.20 or less, more preferably 0.15 or less.
ここで、本実施形態においては、金属粉としては、銀、銅のいずれか一種または二種であることが好ましい。
また、金属粉としては、平均粒径が１００ｎｍ以上３μｍ以下の範囲内であることが好ましい。 Here, in the present embodiment, the metal powder is preferably one or two of silver and copper.
Moreover, it is preferable that the metal powder has an average particle size within the range of 100 nm or more and 3 μm or less.
また、金属粉としては、平均粒径が１００ｎｍ以上３μｍ以下の範囲内であることが好ましい。 Here, in the present embodiment, the metal powder is preferably one or two of silver and copper.
Moreover, it is preferable that the metal powder has an average particle size within the range of 100 nm or more and 3 μm or less.
銅塩は、アミンとともに添加されることで、銅錯体を形成するものであればよい。本実施形態では、銅塩として有機カルボン酸銅塩を用いることが好ましい。具体的には、銅塩として、酢酸銅（II）一水和物、クエン酸銅２．５水和物、２－エチルヘキサン酸銅等を用いることができ、銅塩として酢酸銅（II）一水和物を用いることが好ましい。
なお、本実施形態においては、銅塩として、２種類以上の銅塩を含有していてもよい。 A copper salt may be added together with an amine to form a copper complex. In this embodiment, it is preferable to use an organic carboxylic acid copper salt as the copper salt. Specifically, as the copper salt, copper (II) acetate monohydrate, copper citrate 2.5 hydrate, copper 2-ethylhexanoate, etc. can be used, and as the copper salt, copper (II) acetate It is preferred to use the monohydrate.
In addition, in this embodiment, you may contain two or more types of copper salts as a copper salt.
なお、本実施形態においては、銅塩として、２種類以上の銅塩を含有していてもよい。 A copper salt may be added together with an amine to form a copper complex. In this embodiment, it is preferable to use an organic carboxylic acid copper salt as the copper salt. Specifically, as the copper salt, copper (II) acetate monohydrate, copper citrate 2.5 hydrate, copper 2-ethylhexanoate, etc. can be used, and as the copper salt, copper (II) acetate It is preferred to use the monohydrate.
In addition, in this embodiment, you may contain two or more types of copper salts as a copper salt.
アミンは、銅塩とともに添加されることで、銅錯体を形成するものであればよい。本実施形態では、アミンとして、直鎖アルキルアミンを含むことが好ましい。具体的には、ドデシルアミン、テトラデシルアミン、ステアリンアミン、アミノデカン等を用いることができ、アミンとしてドデシルアミンを用いることが好ましい。
なお、本実施形態においては、アミンとして、２種類以上のアミンを含有していてもよい。 The amine should just form a copper complex by being added with a copper salt. In this embodiment, the amine preferably contains a linear alkylamine. Specifically, dodecylamine, tetradecylamine, stearinamine, aminodecane, etc. can be used, and dodecylamine is preferably used as the amine.
In addition, in this embodiment, two or more types of amines may be contained as amines.
なお、本実施形態においては、アミンとして、２種類以上のアミンを含有していてもよい。 The amine should just form a copper complex by being added with a copper salt. In this embodiment, the amine preferably contains a linear alkylamine. Specifically, dodecylamine, tetradecylamine, stearinamine, aminodecane, etc. can be used, and dodecylamine is preferably used as the amine.
In addition, in this embodiment, two or more types of amines may be contained as amines.
アルコールとしては、グリセリン、α－テルピネオール、ジエチレングリコール（ＤＥＧ）２－エチル１，３―ヘキサンジオール（ＥＨＤ）等を用いることができる。特に、グリセリンを用いることが好ましい。
なお、本実施形態においては、アルコールとして、２種類以上のアルコールを含有していてもよい。 Glycerin, α-terpineol, diethylene glycol (DEG) 2-ethyl 1,3-hexanediol (EHD) and the like can be used as alcohols. In particular, it is preferable to use glycerin.
In addition, in this embodiment, you may contain two or more types of alcohol as alcohol.
なお、本実施形態においては、アルコールとして、２種類以上のアルコールを含有していてもよい。 Glycerin, α-terpineol, diethylene glycol (DEG) 2-
In addition, in this embodiment, you may contain two or more types of alcohol as alcohol.
また、必要に応じて銀塩を含有してもよい。この銀塩は、アミンとともに添加されることで、銀錯体を形成するものであればよい。本実施形態では、銀塩として、酢酸銀、シュウ酸銀、プロピオン酸銀、ミリスチン酸銀、酪酸銀等が挙げられる。特に、酢酸銀を用いることが好ましい。
In addition, it may contain a silver salt as necessary. This silver salt should just form a silver complex by being added with an amine. In this embodiment, silver salts include silver acetate, silver oxalate, silver propionate, silver myristate, silver butyrate, and the like. In particular, it is preferable to use silver acetate.
ここで、金属粉の含有量は、２５ｍａｓｓ％以上７５ｍａｓｓ％以下の範囲内とすることが好ましい。
また、銅塩の含有量は、４ｍａｓｓ％以上１６ｍａｓｓ％以下の範囲内とすることが好ましい。
さらに、アミンの含有量は、１６ｍａｓｓ％以上５４ｍａｓｓ％以下の範囲内とすることが好ましい。
また、アルコールの含有量は、１ｍａｓｓ％以上１０ｍａｓｓ％以下の範囲内とすることが好ましい。
さらに、銀塩を含む場合には、銀塩の含有量は、０．１ｍａｓｓ％以上１２ｍａｓｓ％以下の範囲内とすることが好ましい。
なお、各含有量は、接合用金属ペーストを１００ｍａｓｓ％とした時である。 Here, the content of the metal powder is preferably in the range of 25 mass% or more and 75 mass% or less.
Moreover, it is preferable that the content of the copper salt is within the range of 4 mass % or more and 16 mass % or less.
Furthermore, the content of amine is preferably in the range of 16 mass% or more and 54 mass% or less.
Also, the alcohol content is preferably in the range of 1 mass % or more and 10 mass % or less.
Furthermore, when a silver salt is included, the content of the silver salt is preferably in the range of 0.1 mass % or more and 12 mass % or less.
In addition, each content is when the metal paste for joining is 100 mass%.
また、銅塩の含有量は、４ｍａｓｓ％以上１６ｍａｓｓ％以下の範囲内とすることが好ましい。
さらに、アミンの含有量は、１６ｍａｓｓ％以上５４ｍａｓｓ％以下の範囲内とすることが好ましい。
また、アルコールの含有量は、１ｍａｓｓ％以上１０ｍａｓｓ％以下の範囲内とすることが好ましい。
さらに、銀塩を含む場合には、銀塩の含有量は、０．１ｍａｓｓ％以上１２ｍａｓｓ％以下の範囲内とすることが好ましい。
なお、各含有量は、接合用金属ペーストを１００ｍａｓｓ％とした時である。 Here, the content of the metal powder is preferably in the range of 25 mass% or more and 75 mass% or less.
Moreover, it is preferable that the content of the copper salt is within the range of 4 mass % or more and 16 mass % or less.
Furthermore, the content of amine is preferably in the range of 16 mass% or more and 54 mass% or less.
Also, the alcohol content is preferably in the range of 1 mass % or more and 10 mass % or less.
Furthermore, when a silver salt is included, the content of the silver salt is preferably in the range of 0.1 mass % or more and 12 mass % or less.
In addition, each content is when the metal paste for joining is 100 mass%.
本実施形態の接合用金属ペーストは、上述の金属粉、銅塩、アミン、アルコール、必要に応じて銀塩を、所定の配合となるように秤量し、これらを混合することで製造することができる。
The metal paste for bonding of the present embodiment can be produced by weighing the above-mentioned metal powder, copper salt, amine, alcohol, and optionally silver salt so as to obtain a predetermined composition and mixing them. can.
次に、本実施形態の接合用金属ペーストを用いた接合体の製造方法について、図１および図２を参照して説明する。
本実施形態では、第１部材１１（絶縁回路基板の回路層）と第２部材１２（半導体素子）とが接合層１５を介して接合された接合体１０（半導体装置）を製造するものである。 Next, a method for manufacturing a joined body using the joining metal paste of the present embodiment will be described with reference to FIGS. 1 and 2. FIG.
In this embodiment, a bonded body 10 (semiconductor device) in which a first member 11 (circuit layer of an insulated circuit board) and a second member 12 (semiconductor element) are bonded via abonding layer 15 is manufactured. .
本実施形態では、第１部材１１（絶縁回路基板の回路層）と第２部材１２（半導体素子）とが接合層１５を介して接合された接合体１０（半導体装置）を製造するものである。 Next, a method for manufacturing a joined body using the joining metal paste of the present embodiment will be described with reference to FIGS. 1 and 2. FIG.
In this embodiment, a bonded body 10 (semiconductor device) in which a first member 11 (circuit layer of an insulated circuit board) and a second member 12 (semiconductor element) are bonded via a
（ペースト配設工程Ｓ０１）
まず、図２（ａ）に示すように、第１部材１１と第２部材１２との間に、本実施形態の接合用金属ペースト２０を配設する。
本実施形態では、第１部材１１の接合面に、スクリーン印刷によって、接合用金属ペースト２０を印刷している。また、塗布厚さは、２０μｍ以上５００μｍ以下の範囲内とすることが好ましい。 (Paste arrangement step S01)
First, as shown in FIG. 2( a ), thebonding metal paste 20 of the present embodiment is arranged between the first member 11 and the second member 12 .
In this embodiment, thebonding metal paste 20 is printed on the bonding surface of the first member 11 by screen printing. Moreover, the coating thickness is preferably in the range of 20 μm or more and 500 μm or less.
まず、図２（ａ）に示すように、第１部材１１と第２部材１２との間に、本実施形態の接合用金属ペースト２０を配設する。
本実施形態では、第１部材１１の接合面に、スクリーン印刷によって、接合用金属ペースト２０を印刷している。また、塗布厚さは、２０μｍ以上５００μｍ以下の範囲内とすることが好ましい。 (Paste arrangement step S01)
First, as shown in FIG. 2( a ), the
In this embodiment, the
（液相形成工程Ｓ０２）
次に、第１部材１１と第２部材１２とを接合用金属ペースト２０を介して積層して液相生成温度以上に加熱する。
このとき、３５℃からの昇温過程において、接合用金属ペースト２０に含まれる銅塩とアミンとによって形成される銅錯体が液化し、第１部材１１と第２部材１２との間に液相２１が生成される。これにより、図２（ｂ）に示すように、液相２１の表面張力によって、第１部材１１と第２部材１２との相対位置がセルフアライメントされることになる。
ここで、液相２１の生成温度は３５℃を超え１００℃以下の範囲内であることが好ましい。液相２１の生成温度はより好ましくは１００℃未満である。
また、接合用金属ペースト２０が銀塩を含有する場合には、銀塩とアミンとによって銀錯体が形成されることになる。 (Liquid phase forming step S02)
Next, thefirst member 11 and the second member 12 are laminated via the bonding metal paste 20 and heated to the liquid phase generation temperature or higher.
At this time, in the process of increasing the temperature from 35° C., the copper complex formed by the copper salt and amine contained in thebonding metal paste 20 is liquefied, and a liquid phase is formed between the first member 11 and the second member 12 . 21 is generated. Thereby, as shown in FIG. 2B, the surface tension of the liquid phase 21 causes the relative positions of the first member 11 and the second member 12 to be self-aligned.
Here, the temperature at which theliquid phase 21 is generated is preferably in the range of over 35° C. and 100° C. or less. The formation temperature of the liquid phase 21 is more preferably less than 100°C.
Also, when thebonding metal paste 20 contains a silver salt, a silver complex is formed by the silver salt and the amine.
次に、第１部材１１と第２部材１２とを接合用金属ペースト２０を介して積層して液相生成温度以上に加熱する。
このとき、３５℃からの昇温過程において、接合用金属ペースト２０に含まれる銅塩とアミンとによって形成される銅錯体が液化し、第１部材１１と第２部材１２との間に液相２１が生成される。これにより、図２（ｂ）に示すように、液相２１の表面張力によって、第１部材１１と第２部材１２との相対位置がセルフアライメントされることになる。
ここで、液相２１の生成温度は３５℃を超え１００℃以下の範囲内であることが好ましい。液相２１の生成温度はより好ましくは１００℃未満である。
また、接合用金属ペースト２０が銀塩を含有する場合には、銀塩とアミンとによって銀錯体が形成されることになる。 (Liquid phase forming step S02)
Next, the
At this time, in the process of increasing the temperature from 35° C., the copper complex formed by the copper salt and amine contained in the
Here, the temperature at which the
Also, when the
（液相揮発工程Ｓ０３）
第１部材１１と第２部材１２との相対位置がセルフアライメントされた後、さらに加熱し、一定温度で保持する。保持温度は１００℃以上２００℃以下の範囲内、保持温度での保持時間は５分以上１８０分以下の範囲内とするとよい。保持温度はより好ましくは２００℃未満である。また、液相が一気に揮発しないような温度に設定することが好ましい。
このとき、図２（ｃ）に示すように、アルコールが銅錯体を還元することでナノサイズの銅粒子が生成するとともに、有機成分（銅塩の酸成分、アミン、アルコール）が揮発し、殆どの液相２１が消失する。また、接合用金属ペースト２０が銀塩を含有する場合には、銀塩とアミンとによって形成された銀錯体がアルコールで還元されることで、ナノサイズの銀粒子が生成することになる。 (Liquid phase volatilization step S03)
After the relative positions of thefirst member 11 and the second member 12 are self-aligned, they are further heated and held at a constant temperature. The holding temperature should be in the range of 100° C. or more and 200° C. or less, and the holding time at the holding temperature should be in the range of 5 minutes or more and 180 minutes or less. The holding temperature is more preferably less than 200°C. Moreover, it is preferable to set the temperature so that the liquid phase does not volatilize at once.
At this time, as shown in FIG. 2(c), the alcohol reduces the copper complex to generate nano-sized copper particles, and the organic components (acid component of the copper salt, amine, alcohol) volatilize, of theliquid phase 21 disappears. Moreover, when the bonding metal paste 20 contains a silver salt, the silver complex formed by the silver salt and the amine is reduced with alcohol to generate nano-sized silver particles.
第１部材１１と第２部材１２との相対位置がセルフアライメントされた後、さらに加熱し、一定温度で保持する。保持温度は１００℃以上２００℃以下の範囲内、保持温度での保持時間は５分以上１８０分以下の範囲内とするとよい。保持温度はより好ましくは２００℃未満である。また、液相が一気に揮発しないような温度に設定することが好ましい。
このとき、図２（ｃ）に示すように、アルコールが銅錯体を還元することでナノサイズの銅粒子が生成するとともに、有機成分（銅塩の酸成分、アミン、アルコール）が揮発し、殆どの液相２１が消失する。また、接合用金属ペースト２０が銀塩を含有する場合には、銀塩とアミンとによって形成された銀錯体がアルコールで還元されることで、ナノサイズの銀粒子が生成することになる。 (Liquid phase volatilization step S03)
After the relative positions of the
At this time, as shown in FIG. 2(c), the alcohol reduces the copper complex to generate nano-sized copper particles, and the organic components (acid component of the copper salt, amine, alcohol) volatilize, of the
（焼結工程Ｓ０４）
有機成分が揮発した後、さらに加熱する。加熱温度は液相消失温度よりも高い温度に設定する。ここでの加熱温度は２００℃以上４００℃以下の範囲内、加熱温度での保持時間は１分以上９０分以下の範囲内とするとよい。
このとき、金属粉の焼結が進行し、図２（ｄ）に示すように、金属の焼結体からなる接合層１５が形成される。
なお、接合用金属ペースト２０が銀塩を含有する場合には、ナノサイズの銀粒子が生成することで焼結が十分に進行し、接合強度を向上させることが可能となる。 (Sintering step S04)
After the organic components are volatilized, it is further heated. The heating temperature is set to a temperature higher than the liquid phase disappearance temperature. Here, the heating temperature is preferably in the range of 200° C. or more and 400° C. or less, and the holding time at the heating temperature is preferably in the range of 1 minute or more and 90 minutes or less.
At this time, sintering of the metal powder proceeds, and as shown in FIG.
When the metal paste for bonding 20 contains a silver salt, sintering proceeds sufficiently by generating nano-sized silver particles, and it is possible to improve the bonding strength.
有機成分が揮発した後、さらに加熱する。加熱温度は液相消失温度よりも高い温度に設定する。ここでの加熱温度は２００℃以上４００℃以下の範囲内、加熱温度での保持時間は１分以上９０分以下の範囲内とするとよい。
このとき、金属粉の焼結が進行し、図２（ｄ）に示すように、金属の焼結体からなる接合層１５が形成される。
なお、接合用金属ペースト２０が銀塩を含有する場合には、ナノサイズの銀粒子が生成することで焼結が十分に進行し、接合強度を向上させることが可能となる。 (Sintering step S04)
After the organic components are volatilized, it is further heated. The heating temperature is set to a temperature higher than the liquid phase disappearance temperature. Here, the heating temperature is preferably in the range of 200° C. or more and 400° C. or less, and the holding time at the heating temperature is preferably in the range of 1 minute or more and 90 minutes or less.
At this time, sintering of the metal powder proceeds, and as shown in FIG.
When the metal paste for bonding 20 contains a silver salt, sintering proceeds sufficiently by generating nano-sized silver particles, and it is possible to improve the bonding strength.
以上のような構成とされた本実施形態である接合用金属ペーストによれば、金属粉と銅塩とアミンとアルコールとを含み、１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相が生じる構成とされているので、第１部材１１と第２部材１２との間に、この接合用金属ペースト２０を配設して接合する場合には、接合時の昇温過程において、第１部材１１と第２部材１２との間に液相が生じ、この液相の表面張力により、第１部材１１と第２部材１２との相対位置をセルフアライメントすることができる。なお、金属粉を含有しているので、液相が生じた場合でも、第１部材１１と第２部材１２の間に距離を確保することができ、接合層１５を十分に形成することができる。
According to the bonding metal paste of the present embodiment configured as described above, it contains metal powder, copper salt, amine, and alcohol, and is in the form of a paste within a temperature range of 15° C. or higher and 35° C. or lower, Since a liquid phase is generated in the process of raising the temperature from 35° C., when the metal paste 20 for bonding is disposed between the first member 11 and the second member 12 for bonding, A liquid phase is generated between the first member 11 and the second member 12 in the temperature rising process during bonding, and the surface tension of this liquid phase causes the relative positions of the first member 11 and the second member 12 to be self-aligned. can do. In addition, since the metal powder is contained, even if a liquid phase occurs, a distance can be secured between the first member 11 and the second member 12, and the bonding layer 15 can be sufficiently formed. .
さらに、本実施形態においては、液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成する構成とされているので、焼成後に再度高温環境下に置いても液相が生じず、耐熱性、接合強度に優れた接合層を形成することができる。
また、本実施形態においては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上の範囲内とされているので、銅塩の含有量が確保され、接合時の昇温過程で液相を十分に形成し、セルフアライメントすることができる。さらに、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．２５以下の範囲内とされているので、生成される液相量が過剰にならず、揮発する有機物量が抑制されることで、焼成後の金属焼結体密度が十分高くなり、強い接合強度を実現できる。
さらに、本実施形態においては、アルコールを含んでいるので、接合時の昇温過程において、液相となった銅塩の銅イオンを還元することでナノサイズの銅粒子を生成することができ、銅イオンと錯形成していた有機成分が揮発するようになり液相を確実に消失させることが可能となる。 Furthermore, in the present embodiment, the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body. A bonding layer having excellent heat resistance and bonding strength can be formed without generating a liquid phase even when placed in a high-temperature environment later.
In addition, in the present embodiment, the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is set within a range of 0.02 or more, so that the content of the copper salt is ensured, A sufficient liquid phase is formed in the temperature rising process during bonding, and self-alignment can be achieved. Furthermore, since the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is within the range of 0.25 or less, the amount of the liquid phase generated does not become excessive, and the volatile organic matter By suppressing the amount, the density of the metal sintered body after firing becomes sufficiently high, and high bonding strength can be realized.
Furthermore, in the present embodiment, since alcohol is included, nano-sized copper particles can be generated by reducing the copper ions of the copper salt that has become a liquid phase in the process of increasing the temperature during bonding. The organic component complexed with copper ions is volatilized, and the liquid phase can be reliably eliminated.
また、本実施形態においては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上の範囲内とされているので、銅塩の含有量が確保され、接合時の昇温過程で液相を十分に形成し、セルフアライメントすることができる。さらに、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．２５以下の範囲内とされているので、生成される液相量が過剰にならず、揮発する有機物量が抑制されることで、焼成後の金属焼結体密度が十分高くなり、強い接合強度を実現できる。
さらに、本実施形態においては、アルコールを含んでいるので、接合時の昇温過程において、液相となった銅塩の銅イオンを還元することでナノサイズの銅粒子を生成することができ、銅イオンと錯形成していた有機成分が揮発するようになり液相を確実に消失させることが可能となる。 Furthermore, in the present embodiment, the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body. A bonding layer having excellent heat resistance and bonding strength can be formed without generating a liquid phase even when placed in a high-temperature environment later.
In addition, in the present embodiment, the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is set within a range of 0.02 or more, so that the content of the copper salt is ensured, A sufficient liquid phase is formed in the temperature rising process during bonding, and self-alignment can be achieved. Furthermore, since the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder is within the range of 0.25 or less, the amount of the liquid phase generated does not become excessive, and the volatile organic matter By suppressing the amount, the density of the metal sintered body after firing becomes sufficiently high, and high bonding strength can be realized.
Furthermore, in the present embodiment, since alcohol is included, nano-sized copper particles can be generated by reducing the copper ions of the copper salt that has become a liquid phase in the process of increasing the temperature during bonding. The organic component complexed with copper ions is volatilized, and the liquid phase can be reliably eliminated.
さらに、本実施形態の接合用金属ペーストにおいて、金属粉が銀、銅のいずれか一種または二種である場合には、これらの金属の焼結体からなる接合層１５を形成することができ、熱伝導に特に優れた接合層１５を形成することが可能となる。
Furthermore, in the metal paste for bonding of the present embodiment, when the metal powder is one or both of silver and copper, the bonding layer 15 made of a sintered body of these metals can be formed. It is possible to form the bonding layer 15 that is particularly excellent in heat conduction.
さらに、本実施形態の接合用金属ペーストにおいて、銅塩が有機カルボン酸銅塩を含む場合には、アミンとともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。
Furthermore, in the metal paste for bonding of the present embodiment, when the copper salt contains an organic carboxylic acid copper salt, the metal complex can be reliably formed by adding it together with the amine. A liquid phase can be made to appear reliably.
さらに、本実施形態の接合用金属ペーストにおいては、前記銅塩として、２種類以上の銅塩を含む場合には、単体の銅塩では１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。
Furthermore, in the metal paste for bonding of the present embodiment, when two or more kinds of copper salts are included as the copper salts, the mixture becomes a paste in the temperature range of 15° C. or higher and 35° C. or lower with a single copper salt. Even if not, it is possible to make the mixture into a paste in a temperature range of 15° C. or more and 35° C. or less by combining two or more kinds. Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
また、本実施形態の接合用金属ペーストにおいて、アミンが直鎖アルキルアミンを含む場合には、銅塩とともに添加させることで金属錯体を確実に形成することができ、接合時の昇温過程で確実に液相を出現させることができる。
In addition, in the metal paste for bonding of the present embodiment, when the amine contains a linear alkylamine, the metal complex can be reliably formed by adding it together with the copper salt, and the metal complex can be reliably formed during the temperature rising process during bonding. A liquid phase can appear at
さらに、本実施形態の接合用金属ペーストにおいて、アミンとして、２種類以上のアミンを含む場合には、単体のアミンでは１５℃以上３５℃以下の温度範囲で混合物がペースト状にならないものであっても、２種類以上組み合わせることによって１５℃以上３５℃以下の温度範囲で混合物をペースト状にすることが可能となる。また、組み合わせによって液相生成温度と液相消失温度を調整することが可能となる。
Furthermore, in the metal paste for bonding of the present embodiment, when two or more kinds of amines are included as amines, the mixture does not become a paste in the temperature range of 15° C. or more and 35° C. or less with single amines. Also, by combining two or more kinds, it is possible to make the mixture into a paste in a temperature range of 15° C. or more and 35° C. or less. Moreover, it is possible to adjust the liquid phase formation temperature and the liquid phase disappearance temperature by combining them.
また、本実施形態の接合用金属ペーストにおいて、アルコールとして、２種類以上のアルコールを含む場合には、単体のアルコールではペースト粘度が使用方法によっては最適でないものであっても、２種類以上組み合わせることによってペースト粘度を適した値に調整することが可能となる。
In addition, in the metal paste for bonding of the present embodiment, when two or more types of alcohol are included as the alcohol, even if the paste viscosity is not optimal depending on the method of use with the single alcohol, it is possible to combine two or more types of alcohol. makes it possible to adjust the paste viscosity to a suitable value.
さらに、本実施形態の接合用金属ペーストにおいて、金属粉と銅塩とアミンとアルコールに加えて、さらに銀塩を含んでいる場合には、銀塩がアミンと反応して銀錯体を形成し、この銀錯体をアルコールが還元することでナノサイズの銀粒子が生成することから、接合強度のさらなる向上を図ることが可能となる。
Furthermore, when the metal paste for bonding of the present embodiment contains a silver salt in addition to the metal powder, copper salt, amine, and alcohol, the silver salt reacts with the amine to form a silver complex, Since nano-sized silver particles are generated by reducing the silver complex with alcohol, it is possible to further improve the bonding strength.
本実施形態の接合体１０の製造方法によれば、１５℃以上３５℃以下の温度範囲で第１部材１１と第２部材１２との間に上述の接合用金属ペースト２０を配設し、その後、昇温して液相２１を生じさせているので、液相２１の表面張力によって、第１部材１１と第２部材１２との相対位置をセルフアライメントすることができる。
また、本実施形態においては、液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成しているので、金属焼結体からなる接合層１５を形成でき、耐熱性、接合強度に優れた接合体１０を製造することができる。 According to the method for manufacturing the joined body 10 of the present embodiment, the joiningmetal paste 20 is disposed between the first member 11 and the second member 12 in the temperature range of 15° C. or higher and 35° C. or lower, and then Since the liquid phase 21 is generated by raising the temperature, the relative positions of the first member 11 and the second member 12 can be self-aligned by the surface tension of the liquid phase 21 .
Further, in the present embodiment, the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body. It is possible to form thebonding layer 15 composed of the above, and to manufacture the bonded body 10 having excellent heat resistance and bonding strength.
また、本実施形態においては、液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成しているので、金属焼結体からなる接合層１５を形成でき、耐熱性、接合強度に優れた接合体１０を製造することができる。 According to the method for manufacturing the joined body 10 of the present embodiment, the joining
Further, in the present embodiment, the temperature is raised to the liquid phase generation temperature or higher to cause the liquid phase to disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form the metal sintered body. It is possible to form the
以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。
例えば、本実施形態では、絶縁回路基板の回路層（第１部材）に、電子部品として半導体素子（第２部材）を接合するものとして説明したが、これに限定されることはなく、第１部材および第２部材とが本発明の接合用金属ペーストを用いて接合するものであればよい。 Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the technical idea of the invention.
For example, in the present embodiment, the circuit layer (first member) of the insulated circuit board is described as being joined with a semiconductor element (second member) as an electronic component. It is sufficient that the member and the second member are joined using the joining metal paste of the present invention.
例えば、本実施形態では、絶縁回路基板の回路層（第１部材）に、電子部品として半導体素子（第２部材）を接合するものとして説明したが、これに限定されることはなく、第１部材および第２部材とが本発明の接合用金属ペーストを用いて接合するものであればよい。 Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the technical idea of the invention.
For example, in the present embodiment, the circuit layer (first member) of the insulated circuit board is described as being joined with a semiconductor element (second member) as an electronic component. It is sufficient that the member and the second member are joined using the joining metal paste of the present invention.
以下に、本発明に係る接合用金属ペースト、および、接合体の製造方法の作用効果について評価した評価試験の結果を説明する。
The results of evaluation tests that evaluated the effects of the metal paste for bonding and the method for manufacturing a bonded body according to the present invention will be described below.
（実施例１）
まず、表１，２に示す銅塩とアミンを表１，２に示す比率で混合し、銅塩－アミン混合物を得た。そして、銅塩－アミン混合と、表１，２に示す金属粉、アルコールと、を混合し、本発明例１～１９及び比較例１～１５に係る各種混合物を得た。
表１，２では、使用した金属粉の金属粒径を括弧内に示した。
比較例１１では、Ｓｎ－３．０％Ａｇ－０．５％Ｃｕクリームはんだ（千住金属工業株式会社製）を使用した（表２では、ＳｎＡｇ３Ｃｕ０．５と示す）。
比較例１２では、特許６６４５３１７号の実施例１に記載のあるＣｕコアＳｎシェルペーストを使用した。 (Example 1)
First, copper salts and amines shown in Tables 1 and 2 were mixed at the ratios shown in Tables 1 and 2 to obtain copper salt-amine mixtures. Then, the copper salt-amine mixture was mixed with the metal powder and alcohol shown in Tables 1 and 2 to obtain various mixtures according to Inventive Examples 1-19 and Comparative Examples 1-15.
In Tables 1 and 2, the metal particle size of the metal powder used is shown in parentheses.
In Comparative Example 11, Sn-3.0% Ag-0.5% Cu cream solder (manufactured by Senju Metal Industry Co., Ltd.) was used (shown as SnAg3Cu0.5 in Table 2).
In Comparative Example 12, the Cu core Sn shell paste described in Example 1 of Japanese Patent No. 6645317 was used.
まず、表１，２に示す銅塩とアミンを表１，２に示す比率で混合し、銅塩－アミン混合物を得た。そして、銅塩－アミン混合と、表１，２に示す金属粉、アルコールと、を混合し、本発明例１～１９及び比較例１～１５に係る各種混合物を得た。
表１，２では、使用した金属粉の金属粒径を括弧内に示した。
比較例１１では、Ｓｎ－３．０％Ａｇ－０．５％Ｃｕクリームはんだ（千住金属工業株式会社製）を使用した（表２では、ＳｎＡｇ３Ｃｕ０．５と示す）。
比較例１２では、特許６６４５３１７号の実施例１に記載のあるＣｕコアＳｎシェルペーストを使用した。 (Example 1)
First, copper salts and amines shown in Tables 1 and 2 were mixed at the ratios shown in Tables 1 and 2 to obtain copper salt-amine mixtures. Then, the copper salt-amine mixture was mixed with the metal powder and alcohol shown in Tables 1 and 2 to obtain various mixtures according to Inventive Examples 1-19 and Comparative Examples 1-15.
In Tables 1 and 2, the metal particle size of the metal powder used is shown in parentheses.
In Comparative Example 11, Sn-3.0% Ag-0.5% Cu cream solder (manufactured by Senju Metal Industry Co., Ltd.) was used (shown as SnAg3Cu0.5 in Table 2).
In Comparative Example 12, the Cu core Sn shell paste described in Example 1 of Japanese Patent No. 6645317 was used.
次に、Ａｇでメタライズされた厚み２ｍｍの無酸素銅板上に、上述の混合物を配設した（厚み：５０μｍ、面積：３ｍｍ角）。配設した混合物の上に、厚さ４００μｍで一辺が２．５ｍｍの正方形のＳｉチップ（表面をＡｕメタライズしたもの）をマウントした。マウント位置は、図３（ａ）に示すように、混合物の配設面と素子面の２辺が一致するように調整した。これを加熱して接合層を形成し、無酸素銅板とＳｉチップとを接合した。
得られた混合物および接合状況について、以下の項目を評価した。 Next, the above mixture was placed on a 2 mm thick oxygen-free copper plate metallized with Ag (thickness: 50 μm, area: 3 mm square). A square Si chip with a thickness of 400 μm and a side of 2.5 mm (Au-metallized surface) was mounted on the provided mixture. As shown in FIG. 3A, the mounting position was adjusted so that two sides of the mixture arrangement surface and the element surface were aligned. This was heated to form a bonding layer, and the oxygen-free copper plate and the Si chip were bonded together.
The following items were evaluated for the obtained mixtures and bonding conditions.
得られた混合物および接合状況について、以下の項目を評価した。 Next, the above mixture was placed on a 2 mm thick oxygen-free copper plate metallized with Ag (thickness: 50 μm, area: 3 mm square). A square Si chip with a thickness of 400 μm and a side of 2.5 mm (Au-metallized surface) was mounted on the provided mixture. As shown in FIG. 3A, the mounting position was adjusted so that two sides of the mixture arrangement surface and the element surface were aligned. This was heated to form a bonding layer, and the oxygen-free copper plate and the Si chip were bonded together.
The following items were evaluated for the obtained mixtures and bonding conditions.
ここで、本発明例１－１９，比較例９，１０，１３，１４においては、室温から昇温して、表３および表４に示す液相揮発工程温度で６０分保持し、さらに昇温して、表３および表４に示す焼成工程温度で１５分保持し、その後、室温まで降温した。なお、昇温速度および降温速度は２℃／分とした。
Here, in Examples 1-19 and Comparative Examples 9, 10, 13, and 14 of the present invention, the temperature was raised from room temperature, held at the liquid phase volatilization process temperature shown in Tables 3 and 4 for 60 minutes, and further heated. Then, the temperature in the firing process shown in Tables 3 and 4 was maintained for 15 minutes, and then the temperature was lowered to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 2° C./min.
金属粉としてＳｎＡｇＣｕを用いた比較例１１においては、室温から昇温して、表４に示す液相揮発工程温度で３分保持し、さらに昇温して、表４に示す焼成工程温度で１０秒保持し、その後、室温まで降温した。なお、昇温速度および降温速度は３０℃／分とした。また、液相生成温度をＳｎＡｇＣｕの溶融温度とし、液相消失温度をフラックスの揮発温度とした。
In Comparative Example 11 using SnAgCu as the metal powder, the temperature was raised from room temperature, held at the liquid phase volatilization process temperature shown in Table 4 for 3 minutes, and further heated to 10 minutes at the firing process temperature shown in Table 4. The temperature was maintained for a second and then cooled to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 30° C./min. Also, the melting temperature of SnAgCu was taken as the liquid phase formation temperature, and the volatilization temperature of the flux was taken as the liquid phase disappearance temperature.
金属粉としてＣｕコアＳｎシェルを用いた比較例１２においては、室温から昇温して、表４に示す液相揮発工程温度で３分保持し、さらに昇温して、表４に示す焼成工程温度で１０秒保持し、その後、室温まで降温した。なお、昇温速度および降温速度は３０℃／分とした。また、液相生成温度をＳｎの融点とし、液相消失温度をフラックスの揮発温度とした。
In Comparative Example 12 using a Cu core and Sn shell as the metal powder, the temperature was raised from room temperature, the liquid phase volatilization process temperature shown in Table 4 was maintained for 3 minutes, and the temperature was further raised to perform the firing process shown in Table 4. The temperature was held for 10 seconds and then cooled to room temperature. The rate of temperature increase and the rate of temperature decrease were set to 30° C./min. Also, the melting point of Sn was taken as the liquid phase formation temperature, and the volatilization temperature of the flux was taken as the liquid phase disappearance temperature.
（１５℃－３５℃での性状）
得られた各混合物を目視にて確認し、粉末状の残留物が確認される場合（いわゆるぼそぼその状態である場合）を「粉状」とした。「粉状」であった混合物以外の各混合物については、粘度をレオメータ（ＴＡインスツルメント製ＤＨＲ－３）により、測定温度を１５℃および３５℃とし、せん断速度を１０（１／ｓ）として測定した。１５℃および３５℃いずれの粘度も１０Ｐａ・ｓ以上５００Ｐａ・ｓ以下であるものを「ペースト状」であるとし、いずれかの温度での測定で１０Ｐａ・ｓ未満であるものを「液状」であるとした。 (Properties at 15°C-35°C)
Each of the resulting mixtures was visually observed, and when powdery residue was observed (so-called crumbly state), it was defined as "powdery". For each mixture other than the "powder" mixture, the viscosity was measured with a rheometer (TA Instruments DHR-3) at temperatures of 15 ° C. and 35 ° C. and a shear rate of 10 (1 / s). It was measured. If the viscosity at both 15 ° C. and 35 ° C. is 10 Pa s or more and 500 Pa s or less, it is “paste”, and if it is less than 10 Pa s at any temperature, it is “liquid”. and
得られた各混合物を目視にて確認し、粉末状の残留物が確認される場合（いわゆるぼそぼその状態である場合）を「粉状」とした。「粉状」であった混合物以外の各混合物については、粘度をレオメータ（ＴＡインスツルメント製ＤＨＲ－３）により、測定温度を１５℃および３５℃とし、せん断速度を１０（１／ｓ）として測定した。１５℃および３５℃いずれの粘度も１０Ｐａ・ｓ以上５００Ｐａ・ｓ以下であるものを「ペースト状」であるとし、いずれかの温度での測定で１０Ｐａ・ｓ未満であるものを「液状」であるとした。 (Properties at 15°C-35°C)
Each of the resulting mixtures was visually observed, and when powdery residue was observed (so-called crumbly state), it was defined as "powdery". For each mixture other than the "powder" mixture, the viscosity was measured with a rheometer (TA Instruments DHR-3) at temperatures of 15 ° C. and 35 ° C. and a shear rate of 10 (1 / s). It was measured. If the viscosity at both 15 ° C. and 35 ° C. is 10 Pa s or more and 500 Pa s or less, it is “paste”, and if it is less than 10 Pa s at any temperature, it is “liquid”. and
（液相生成の有無／液相生成温度）
熱重量示差熱分析（ＴＧ－ＤＴＡ）（ＮＥＴＺＳＣＨ社、ＳＴＡ－２５００ Ｒｅｇｕｌｕｓ）を用いて測定した。得られた各混合物について、窒素雰囲気、１０℃／分の昇温速度、２５℃から５００℃まで示差熱分析を行った。ＴＧカーブで重量減少が見られず、且つ、ＤＴＡカーブにおいて吸熱ピークが見られる場合を液相が生成したと判断した。
表３、４では、液相が生成したと判断されるものについて「有」とし、液相が生じず液状の状態を維持しているものについて「液状のまま」とし、液相が生じなかったものについて「無」と表示した。
液相生成温度は、図４に示されるようにＤＴＡカーブのピークから低温部（低温側）に向かって引いた接線がＤＴＡカーブの平らな部分の延長線と交わる点の温度とした。 (Presence or absence of liquid phase generation/liquid phase generation temperature)
It was measured using thermogravimetric differential thermal analysis (TG-DTA) (STA-2500 Regulus, NETZSCH). Differential thermal analysis was performed on each of the obtained mixtures from 25° C. to 500° C. in a nitrogen atmosphere at a heating rate of 10° C./min. It was determined that a liquid phase was formed when no weight reduction was observed on the TG curve and an endothermic peak was observed on the DTA curve.
In Tables 3 and 4, those judged to have generated a liquid phase were rated as "present", and those that did not generate a liquid phase and remained in a liquid state were rated as "remained in a liquid state", and no liquid phase was generated. "None" was displayed for the item.
The liquid phase formation temperature was the temperature at the point where the tangent line drawn from the peak of the DTA curve toward the low temperature portion (low temperature side) intersects with the extended line of the flat portion of the DTA curve, as shown in FIG.
熱重量示差熱分析（ＴＧ－ＤＴＡ）（ＮＥＴＺＳＣＨ社、ＳＴＡ－２５００ Ｒｅｇｕｌｕｓ）を用いて測定した。得られた各混合物について、窒素雰囲気、１０℃／分の昇温速度、２５℃から５００℃まで示差熱分析を行った。ＴＧカーブで重量減少が見られず、且つ、ＤＴＡカーブにおいて吸熱ピークが見られる場合を液相が生成したと判断した。
表３、４では、液相が生成したと判断されるものについて「有」とし、液相が生じず液状の状態を維持しているものについて「液状のまま」とし、液相が生じなかったものについて「無」と表示した。
液相生成温度は、図４に示されるようにＤＴＡカーブのピークから低温部（低温側）に向かって引いた接線がＤＴＡカーブの平らな部分の延長線と交わる点の温度とした。 (Presence or absence of liquid phase generation/liquid phase generation temperature)
It was measured using thermogravimetric differential thermal analysis (TG-DTA) (STA-2500 Regulus, NETZSCH). Differential thermal analysis was performed on each of the obtained mixtures from 25° C. to 500° C. in a nitrogen atmosphere at a heating rate of 10° C./min. It was determined that a liquid phase was formed when no weight reduction was observed on the TG curve and an endothermic peak was observed on the DTA curve.
In Tables 3 and 4, those judged to have generated a liquid phase were rated as "present", and those that did not generate a liquid phase and remained in a liquid state were rated as "remained in a liquid state", and no liquid phase was generated. "None" was displayed for the item.
The liquid phase formation temperature was the temperature at the point where the tangent line drawn from the peak of the DTA curve toward the low temperature portion (low temperature side) intersects with the extended line of the flat portion of the DTA curve, as shown in FIG.
（液相の消失／液相消失温度）
液相生成の有無を判断した時と同じ測定装置及び条件により５００℃まで測定し、ＴＧカーブにおいて、３００℃までにアルコール添加量又はフラックス添加量以上の重量減少が確認された場合を液相が消失したとして「Ａ」、重量減少量がアルコール添加量又はフラックス添加量未満であった場合を液相が残っているとして「Ｂ」とした。
液相消失温度は、ＴＧカーブにおいて重量減少時の接線が、重量減少が終わった定常状態の直線の延長線と交わる点の温度とした。 (Disappearance of liquid phase/disappearance temperature of liquid phase)
Measurement was carried out up to 500°C using the same measuring equipment and conditions as when judging the presence or absence of liquid phase formation, and the liquid phase was confirmed when a weight decrease equal to or greater than the amount of alcohol or flux added was confirmed up to 300°C on the TG curve. "A" was given when it disappeared, and "B" was given when the amount of weight loss was less than the amount of alcohol added or the amount of flux added because the liquid phase remained.
The liquid phase disappearance temperature was taken as the temperature at the point where the tangent line at the time of weight reduction in the TG curve intersects with the extension of the straight line in the steady state after weight reduction.
液相生成の有無を判断した時と同じ測定装置及び条件により５００℃まで測定し、ＴＧカーブにおいて、３００℃までにアルコール添加量又はフラックス添加量以上の重量減少が確認された場合を液相が消失したとして「Ａ」、重量減少量がアルコール添加量又はフラックス添加量未満であった場合を液相が残っているとして「Ｂ」とした。
液相消失温度は、ＴＧカーブにおいて重量減少時の接線が、重量減少が終わった定常状態の直線の延長線と交わる点の温度とした。 (Disappearance of liquid phase/disappearance temperature of liquid phase)
Measurement was carried out up to 500°C using the same measuring equipment and conditions as when judging the presence or absence of liquid phase formation, and the liquid phase was confirmed when a weight decrease equal to or greater than the amount of alcohol or flux added was confirmed up to 300°C on the TG curve. "A" was given when it disappeared, and "B" was given when the amount of weight loss was less than the amount of alcohol added or the amount of flux added because the liquid phase remained.
The liquid phase disappearance temperature was taken as the temperature at the point where the tangent line at the time of weight reduction in the TG curve intersects with the extension of the straight line in the steady state after weight reduction.
（セルフアライメント）
焼成を行った後に、接合材とチップで隣接する辺の距離を測定し、図３（ｂ）に示すように、４辺全てで０．２ｍｍ以上の距離があればアライメント性有りとして「Ａ」とし、図３（ｃ）に示すように、１辺でも０．２ｍｍ未満の距離であればアライメント性無しとして「Ｂ」とした。 (self alignment)
After firing, the distance between adjacent sides of the bonding material and the chip was measured, and as shown in FIG. As shown in FIG. 3(c), if even one side had a distance of less than 0.2 mm, it was judged as having no alignment property and was rated as "B".
焼成を行った後に、接合材とチップで隣接する辺の距離を測定し、図３（ｂ）に示すように、４辺全てで０．２ｍｍ以上の距離があればアライメント性有りとして「Ａ」とし、図３（ｃ）に示すように、１辺でも０．２ｍｍ未満の距離であればアライメント性無しとして「Ｂ」とした。 (self alignment)
After firing, the distance between adjacent sides of the bonding material and the chip was measured, and as shown in FIG. As shown in FIG. 3(c), if even one side had a distance of less than 0.2 mm, it was judged as having no alignment property and was rated as "B".
（シェア強度）
接合強度は、せん断強度評価試験機(ＴＲＹ ＰＲＥＳＩＣＩＯＮ社製ＭＦＭ １５００ＨＦ)を用いて測定した。
具体的には、接合強度の測定は、接合体の無酸素銅板を水平に固定し、接合層の表面（上面）から５０μｍ上方の位置でシェアツールにより、接合体のＳｉチップを横から水平方向に押して、Ｓｉチップが破断されたときの強度を測定することによって行った。なお、シェアツールの移動速度は０．１ｍｍ／秒とした。１条件に付き３回強度試験を行い、それらの算術平均値を接合強度の測定値とした。 (Share strength)
The bonding strength was measured using a shear strength evaluation tester (MFM 1500HF manufactured by TRY PRESICION).
Specifically, the bonding strength was measured by fixing the oxygen-free copper plate of the bonded body horizontally, and moving the Si chip of the bonded body horizontally from the side with a shear tool at a position 50 μm above the surface (upper surface) of the bonding layer. , and measured the strength when the Si chip was broken. In addition, the moving speed of the share tool was set to 0.1 mm/sec. The strength test was performed three times per condition, and the arithmetic mean value thereof was used as the measurement value of the bonding strength.
接合強度は、せん断強度評価試験機(ＴＲＹ ＰＲＥＳＩＣＩＯＮ社製ＭＦＭ １５００ＨＦ)を用いて測定した。
具体的には、接合強度の測定は、接合体の無酸素銅板を水平に固定し、接合層の表面（上面）から５０μｍ上方の位置でシェアツールにより、接合体のＳｉチップを横から水平方向に押して、Ｓｉチップが破断されたときの強度を測定することによって行った。なお、シェアツールの移動速度は０．１ｍｍ／秒とした。１条件に付き３回強度試験を行い、それらの算術平均値を接合強度の測定値とした。 (Share strength)
The bonding strength was measured using a shear strength evaluation tester (MFM 1500HF manufactured by TRY PRESICION).
Specifically, the bonding strength was measured by fixing the oxygen-free copper plate of the bonded body horizontally, and moving the Si chip of the bonded body horizontally from the side with a shear tool at a position 50 μm above the surface (upper surface) of the bonding layer. , and measured the strength when the Si chip was broken. In addition, the moving speed of the share tool was set to 0.1 mm/sec. The strength test was performed three times per condition, and the arithmetic mean value thereof was used as the measurement value of the bonding strength.
（耐熱性評価）
焼成後のサンプルについて、冷熱衝撃試験機（エスペック社製ＴＳＥ－１１－Ａ）を用いて１７５℃にて１５分加熱後、－４０℃に降温して１５分冷却後、さらに１７５℃に昇温する過程を１サイクルとする熱衝撃試験を１００サイクル実施した。
超音波映像装置（日立パワーソリューションズ社製ＦＳＰ８Ｖ）を用い、無酸素銅板とＳｉチップが接合層で接合されている部分を確認するために撮像した。使用したトランデューサー（プローブ）は周波数１４０ＭＨｚである。撮影した像から剥離している面積を求め、剥離面積がチップ面積の１０％未満であるものを「Ａ」、１０％以上であるものを「Ｂ」とした。なお、超音波映像装置による像では、Ｓｉチップと無酸素銅板が剥離をしている部分は白、接合している部分は灰色に見える。 (Heat resistance evaluation)
The sample after firing was heated at 175°C for 15 minutes using a thermal shock tester (TSE-11-A manufactured by Espec Co., Ltd.), cooled to -40°C for 15 minutes, and then heated to 175°C. A thermal shock test was conducted for 100 cycles, in which one cycle is the process of
Using an ultrasonic imaging device (FSP8V manufactured by Hitachi Power Solutions Co., Ltd.), an image was taken to confirm the portion where the oxygen-free copper plate and the Si chip were bonded by the bonding layer. The transducer (probe) used has a frequency of 140 MHz. The peeled area was determined from the photographed image, and "A" was given when the peeled area was less than 10% of the chip area, and "B" was given when it was 10% or more. In the image obtained by the ultrasonic imaging device, the part where the Si chip and the oxygen-free copper plate are peeled off looks white, and the part where they are joined looks gray.
焼成後のサンプルについて、冷熱衝撃試験機（エスペック社製ＴＳＥ－１１－Ａ）を用いて１７５℃にて１５分加熱後、－４０℃に降温して１５分冷却後、さらに１７５℃に昇温する過程を１サイクルとする熱衝撃試験を１００サイクル実施した。
超音波映像装置（日立パワーソリューションズ社製ＦＳＰ８Ｖ）を用い、無酸素銅板とＳｉチップが接合層で接合されている部分を確認するために撮像した。使用したトランデューサー（プローブ）は周波数１４０ＭＨｚである。撮影した像から剥離している面積を求め、剥離面積がチップ面積の１０％未満であるものを「Ａ」、１０％以上であるものを「Ｂ」とした。なお、超音波映像装置による像では、Ｓｉチップと無酸素銅板が剥離をしている部分は白、接合している部分は灰色に見える。 (Heat resistance evaluation)
The sample after firing was heated at 175°C for 15 minutes using a thermal shock tester (TSE-11-A manufactured by Espec Co., Ltd.), cooled to -40°C for 15 minutes, and then heated to 175°C. A thermal shock test was conducted for 100 cycles, in which one cycle is the process of
Using an ultrasonic imaging device (FSP8V manufactured by Hitachi Power Solutions Co., Ltd.), an image was taken to confirm the portion where the oxygen-free copper plate and the Si chip were bonded by the bonding layer. The transducer (probe) used has a frequency of 140 MHz. The peeled area was determined from the photographed image, and "A" was given when the peeled area was less than 10% of the chip area, and "B" was given when it was 10% or more. In the image obtained by the ultrasonic imaging device, the part where the Si chip and the oxygen-free copper plate are peeled off looks white, and the part where they are joined looks gray.
比較例１，２，４－６においては、１５℃以上３５℃以下の温度範囲で粉状であり、無酸素銅板に混合物を印刷することができなかった。このため、セルフアライメント、耐熱性、シェア強度を評価しなかった。
比較例３，７，８，１５においては、１５℃以上３５℃以下の温度範囲で液状であり、無酸素銅板に混合物を印刷することができなかった。このため、セルフアライメント、耐熱性、シェア強度を評価しなかった。 In Comparative Examples 1, 2, and 4-6, the mixture was powdery in the temperature range of 15° C. or higher and 35° C. or lower, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
In Comparative Examples 3, 7, 8, and 15, the mixture was liquid in the temperature range of 15° C. or more and 35° C. or less, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
比較例３，７，８，１５においては、１５℃以上３５℃以下の温度範囲で液状であり、無酸素銅板に混合物を印刷することができなかった。このため、セルフアライメント、耐熱性、シェア強度を評価しなかった。 In Comparative Examples 1, 2, and 4-6, the mixture was powdery in the temperature range of 15° C. or higher and 35° C. or lower, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
In Comparative Examples 3, 7, 8, and 15, the mixture was liquid in the temperature range of 15° C. or more and 35° C. or less, and the mixture could not be printed on the oxygen-free copper plate. Therefore, self-alignment, heat resistance, and shear strength were not evaluated.
比較例９においては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．０１とされており、銅塩の含有量が不足しており、液相が十分に形成されず、セルフアライメントが「Ｂ」となった。
比較例１０においては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．２７とされており、揮発した有機物量が多いために接合層の金属焼結体密度が低くなり、接合強度（シェア強度）が低くなった。 In Comparative Example 9, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder was 0.01, and the content of the copper salt was insufficient, and the liquid phase was sufficiently It was not formed and the self-alignment was "B".
In Comparative Example 10, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder was set to 0.27. became lower, and the joint strength (shear strength) became lower.
比較例１０においては、銅塩中のＣｕ重量Ａと金属粉の重量Ｂとの比Ａ／Ｂが０．２７とされており、揮発した有機物量が多いために接合層の金属焼結体密度が低くなり、接合強度（シェア強度）が低くなった。 In Comparative Example 9, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder was 0.01, and the content of the copper salt was insufficient, and the liquid phase was sufficiently It was not formed and the self-alignment was "B".
In Comparative Example 10, the ratio A/B between the weight A of Cu in the copper salt and the weight B of the metal powder was set to 0.27. became lower, and the joint strength (shear strength) became lower.
比較例１１，１２においては、Ｃｕ－Ｓｎ系のはんだ材とされており、耐熱性が不十分であった。
比較例１３においては、銅塩を有していないＡｇペーストとされており、昇温過程で液相が生じず、セルフアライメントが「Ｂ」となった。
比較例１４においては、焼成工程温度が液相消失温度よりも低く、金属焼結体からなる接合層の内部に有機成分が残存し、接合強度が低くなった。 In Comparative Examples 11 and 12, Cu—Sn based solder materials were used, and the heat resistance was insufficient.
In Comparative Example 13, an Ag paste containing no copper salt was used, and no liquid phase was generated during the temperature rising process, resulting in self-alignment of "B".
In Comparative Example 14, the firing process temperature was lower than the liquid phase disappearance temperature, organic components remained inside the bonding layer made of the sintered metal, and the bonding strength was low.
比較例１３においては、銅塩を有していないＡｇペーストとされており、昇温過程で液相が生じず、セルフアライメントが「Ｂ」となった。
比較例１４においては、焼成工程温度が液相消失温度よりも低く、金属焼結体からなる接合層の内部に有機成分が残存し、接合強度が低くなった。 In Comparative Examples 11 and 12, Cu—Sn based solder materials were used, and the heat resistance was insufficient.
In Comparative Example 13, an Ag paste containing no copper salt was used, and no liquid phase was generated during the temperature rising process, resulting in self-alignment of "B".
In Comparative Example 14, the firing process temperature was lower than the liquid phase disappearance temperature, organic components remained inside the bonding layer made of the sintered metal, and the bonding strength was low.
これに対して、本発明例１－１９においては、金属粉と銅塩とアミンとを含み、１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相が生じ、液相生成温度以上の昇温過程で液相が消失し、液相消失温度以上で金属焼結体を形成するものとされており、セルフアライメントが「Ａ」となるとともに、耐熱性、接合強度に優れていた。
On the other hand, Inventive Example 1-19 contains a metal powder, a copper salt and an amine, is in a paste form within the temperature range of 15° C. or higher and 35° C. or lower, and becomes liquid in the process of raising the temperature from 35° C. A phase is generated, and the liquid phase disappears in the process of raising the temperature above the liquid phase generation temperature, and the metal sintered body is formed at the liquid phase disappearance temperature or higher. It was excellent in durability and bonding strength.
以上のことから、本発明例によれば、接合時の昇温過程において液相を生じさせ、セルフアライメントによって部材同士の相対位置の位置調整を行うことができ、かつ、耐熱性、接合強度に優れた接合層を形成可能な接合用金属ペースト、および、接合体の製造方法を提供可能であることが確認された。
From the above, according to the example of the present invention, a liquid phase is generated in the temperature rising process at the time of bonding, and the relative positions of the members can be adjusted by self-alignment, and heat resistance and bonding strength can be improved. It was confirmed that it is possible to provide a bonding metal paste capable of forming an excellent bonding layer and a method for manufacturing a bonded body.
（実施例２）
表１に示す本発明例２の接合用金属ペーストに、銀塩（酢酸銀）を４ｍａｓｓ％添加したものを、本発明例２０とした。
次に、最表面がＡｇでメタライズされた厚み２ｍｍの無酸素銅板（以下、Ａｇメタライズ銅板）を準備した。 (Example 2)
Inventive Example 20 was obtained by adding 4 mass % of a silver salt (silver acetate) to the joining metal paste of Inventive Example 2 shown in Table 1.
Next, an oxygen-free copper plate having a thickness of 2 mm whose outermost surface was metallized with Ag (hereinafter referred to as Ag-metallized copper plate) was prepared.
表１に示す本発明例２の接合用金属ペーストに、銀塩（酢酸銀）を４ｍａｓｓ％添加したものを、本発明例２０とした。
次に、最表面がＡｇでメタライズされた厚み２ｍｍの無酸素銅板（以下、Ａｇメタライズ銅板）を準備した。 (Example 2)
Inventive Example 20 was obtained by adding 4 mass % of a silver salt (silver acetate) to the joining metal paste of Inventive Example 2 shown in Table 1.
Next, an oxygen-free copper plate having a thickness of 2 mm whose outermost surface was metallized with Ag (hereinafter referred to as Ag-metallized copper plate) was prepared.
このＡｇメタライズ層の上に、本発明例２、および、本発明例２０の接合用金属ペーストを配設した（厚み：１００μｍ、面積：３ｍｍ角）。配設した混合物の上に、厚さ２．５ｍｍで一辺が２．５ｍｍの正方形のＳｉチップ（表面をＡｕメタライズしたもの）をマウントした。これを加熱して接合層を形成し、無酸素銅板とＳｉチップとを接合した。ここで、液相揮発工程の加熱温度および保持時間、焼成工程の加熱温度および保持時間を表５に示す条件とした。
そして、実施例１と同様の手順にて、シェア強度を測定した。測定結果を表５に示す。 On this Ag metallized layer, the bonding metal pastes of Inventive Example 2 and Inventive Example 20 were arranged (thickness: 100 μm, area: 3 mm square). A square Si chip with a thickness of 2.5 mm and a side of 2.5 mm (Au-metallized surface) was mounted on the provided mixture. This was heated to form a bonding layer, and the oxygen-free copper plate and the Si chip were bonded together. Here, the conditions shown in Table 5 were set for the heating temperature and holding time in the liquid phase volatilization step, and the heating temperature and holding time in the firing step.
Then, the shear strength was measured in the same procedure as in Example 1. Table 5 shows the measurement results.
そして、実施例１と同様の手順にて、シェア強度を測定した。測定結果を表５に示す。 On this Ag metallized layer, the bonding metal pastes of Inventive Example 2 and Inventive Example 20 were arranged (thickness: 100 μm, area: 3 mm square). A square Si chip with a thickness of 2.5 mm and a side of 2.5 mm (Au-metallized surface) was mounted on the provided mixture. This was heated to form a bonding layer, and the oxygen-free copper plate and the Si chip were bonded together. Here, the conditions shown in Table 5 were set for the heating temperature and holding time in the liquid phase volatilization step, and the heating temperature and holding time in the firing step.
Then, the shear strength was measured in the same procedure as in Example 1. Table 5 shows the measurement results.
表５に示すように、銀塩を添加した本発明例２０の接合用金属ペーストにおいては、銀塩を添加していない本発明例２の接合用金属ペーストに比べて、シェア強度が向上することが確認された。
As shown in Table 5, the metal paste for bonding of Inventive Example 20 to which a silver salt is added has an improved shear strength compared to the metal paste for bonding of Inventive Example 2 to which no silver salt is added. was confirmed.
Claims (9)
- 金属粉と銅塩とアミンとアルコールとを含み、前記銅塩中のＣｕ重量Ａと前記金属粉の重量Ｂとの比Ａ／Ｂが０．０２以上０．２５以下の範囲内とされており、
１５℃以上３５℃以下の温度範囲内でペースト状であり、３５℃からの昇温過程で液相が生成し、液相生成温度以上の昇温過程で液相が消失し、液相消失温度以上で金属焼結体を形成することを特徴とする接合用金属ペースト。 It contains a metal powder, a copper salt, an amine, and an alcohol, and the ratio A/B of the weight A of Cu in the copper salt to the weight B of the metal powder is in the range of 0.02 or more and 0.25 or less. ,
It is pasty within the temperature range of 15°C or higher and 35°C or lower, and a liquid phase is generated in the process of increasing the temperature from 35°C, and the liquid phase disappears in the process of increasing the temperature above the liquid phase generation temperature, and the liquid phase disappears temperature. A metal paste for bonding, characterized by forming a metal sintered body as described above. - 前記金属粉は、銀、銅のいずれか一種または二種であることを特徴とする請求項１に記載の接合用金属ペースト。 The metal paste for bonding according to claim 1, wherein the metal powder is one or two of silver and copper.
- 前記銅塩は、有機カルボン酸銅塩を含むことを特徴とする請求項１または請求項２に記載の接合用金属ペースト。 The metal paste for bonding according to claim 1 or 2, wherein the copper salt contains an organic carboxylic acid copper salt.
- 前記銅塩が２種類以上の銅塩から成ることを特徴とする請求項１から請求項３のいずれか一項に記載の接合用金属ペースト。 The metal paste for bonding according to any one of claims 1 to 3, wherein the copper salt is composed of two or more kinds of copper salts.
- 前記アミンが直鎖アルキルアミンを含むことを特徴とする請求項１から請求項４のいずれか一項に記載の接合用金属ペースト。 The metal paste for bonding according to any one of claims 1 to 4, wherein the amine contains a linear alkylamine.
- 前記アミンが２種類以上のアミンから成ることを特徴とする請求項１から請求項５のいずれか一項に記載の接合用金属ペースト。 The metal paste for bonding according to any one of claims 1 to 5, wherein the amine is composed of two or more types of amine.
- 前記アルコールが２種類以上のアルコールから成ることを特徴とする請求項１から請求項６のいずれか一項に記載の接合用金属ペースト。 The metal paste for bonding according to any one of claims 1 to 6, wherein the alcohol is composed of two or more types of alcohol.
- さらに銀塩を含むことを特徴とする請求項１から請求項７のいずれか一項に記載の接合用金属ペースト。 The joining metal paste according to any one of claims 1 to 7, further comprising a silver salt.
- 第１部材と第２部材とが接合された接合体の製造方法であって、
１５℃以上３５℃以下の温度範囲で、前記第１部材と前記第２部材との間に、請求項１から請求項８のいずれか一項に記載の接合用金属ペーストを配設し、
前記第１部材と前記第２部材との間に前記接合用金属ペーストを配設した状態で昇温して、前記第１部材と前記第２部材との間に液相を生じさせ、
さらに液相生成温度以上に昇温して液相を消失させ、さらに液相消失温度以上に昇温して金属焼結体を形成し、前記第１部材と前記第２部材とを接合することを特徴とする接合体の製造方法。 A method for manufacturing a joined body in which a first member and a second member are joined,
Disposing the bonding metal paste according to any one of claims 1 to 8 between the first member and the second member at a temperature range of 15 ° C. or higher and 35 ° C. or lower,
raising the temperature in a state where the metal paste for bonding is disposed between the first member and the second member to generate a liquid phase between the first member and the second member;
Furthermore, the temperature is raised to the liquid phase generation temperature or higher to make the liquid phase disappear, and the temperature is further raised to the liquid phase disappearance temperature or higher to form a metal sintered body and join the first member and the second member. A method for producing a joined body, characterized by:
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| JP2023511696A JP7568068B2 (en) | 2021-04-01 | 2022-03-31 | Metal paste for bonding and method for manufacturing bonded body |
| US18/284,338 US20240149344A1 (en) | 2021-04-01 | 2022-03-31 | Metal paste for bonding, and method for manufacturing bonded body |
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| JP2021-062770 | 2021-04-01 | ||
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| PCT/JP2022/016454 WO2022211008A1 (en) | 2021-04-01 | 2022-03-31 | Metal paste for joining, and method for manufacturing joined body |
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| Country | Link |
|---|---|
| US (1) | US20240149344A1 (en) |
| JP (1) | JP7568068B2 (en) |
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| WO (1) | WO2022211008A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6428339A (en) | 1987-07-23 | 1989-01-30 | Showa Aluminum Corp | Aluminum casting alloy for intake manifold |
| JP2000271782A (en) | 1999-03-24 | 2000-10-03 | Matsushita Electric Ind Co Ltd | Metal paste for soldering and soldering method |
| JP2014186902A (en) * | 2013-03-25 | 2014-10-02 | Fujifilm Corp | Production method of conductive film |
| JP2019070174A (en) * | 2017-10-06 | 2019-05-09 | 株式会社豊田中央研究所 | Bonding paste and semiconductor device using same |
| WO2020004342A1 (en) * | 2018-06-25 | 2020-01-02 | 三菱マテリアル株式会社 | Silver paste and joined body production method |
| JP2021062770A (en) | 2019-10-15 | 2021-04-22 | 森六テクノロジー株式会社 | Blowout port device for air conditioning |
-
2022
- 2022-03-31 JP JP2023511696A patent/JP7568068B2/en active Active
- 2022-03-31 WO PCT/JP2022/016454 patent/WO2022211008A1/en active Application Filing
- 2022-03-31 US US18/284,338 patent/US20240149344A1/en active Pending
- 2022-04-01 TW TW111112765A patent/TW202302252A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6428339A (en) | 1987-07-23 | 1989-01-30 | Showa Aluminum Corp | Aluminum casting alloy for intake manifold |
| JP2000271782A (en) | 1999-03-24 | 2000-10-03 | Matsushita Electric Ind Co Ltd | Metal paste for soldering and soldering method |
| JP2014186902A (en) * | 2013-03-25 | 2014-10-02 | Fujifilm Corp | Production method of conductive film |
| JP2019070174A (en) * | 2017-10-06 | 2019-05-09 | 株式会社豊田中央研究所 | Bonding paste and semiconductor device using same |
| WO2020004342A1 (en) * | 2018-06-25 | 2020-01-02 | 三菱マテリアル株式会社 | Silver paste and joined body production method |
| JP2021062770A (en) | 2019-10-15 | 2021-04-22 | 森六テクノロジー株式会社 | Blowout port device for air conditioning |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202302252A (en) | 2023-01-16 |
| US20240149344A1 (en) | 2024-05-09 |
| JP7568068B2 (en) | 2024-10-16 |
| JPWO2022211008A1 (en) | 2022-10-06 |
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